Triarylphosphine or triarylarsine compound, alpha-olefin polymerization catalyst using the compound, ternary copolymer, and production process of alpha-olefin-((meth)acrylic acid)-based copolymer

ABSTRACT

To provide an industrially useful α-olefin•((meth)acrylic acid)-based olefin copolymer having both a high molecular weight and a high comonomer content, a catalyst component capable of realizing a production of two different kinds of α-olefin•((meth)acrylic acid)-based olefin copolymers, and a production process using the catalyst. An α-olefin•((meth)acrylic acid)-based olefin copolymer is produced by using a metal complex complexed with a ligand represented by the following formula (Y is phosphorus or arsenic) for a catalyst composition.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a Divisional of U.S. application Ser. No.13/130,494, filed Jun. 2, 2011, now allowed.

TECHNICAL FIELD

The present invention relates to a novel triarylphosphine ortriarylarsine compound, an α-olefin polymerization catalyst using thecompound, and a production process of an α-olefin•((meth)acrylicacid)-based copolymer. More specifically, the present invention relatesto an α-olefin•((meth)acrylic acid)-based ternary copolymer having botha high molecular weight and a high comonomer content, and a productionprocess thereof, which are realized by virtue of an α-olefin-basedpolymerization catalyst using the novel compound above.

BACKGROUND ART

Out of resin materials, an ethylene polymer and an ethylene-basedpolymer such as copolymer of an ethylene and an α-olefin are excellentin the physical properties or various properties such as moldability andhave a superiority in view of profitability, environmental complianceand the like, and these materials have been heretofore very widelyemployed for general purposes and are being used as an importantindustrial material. However, the ethylene-based polymer has no polargroup and its application to the field requiring physical propertiessuch as adhesion to another material, printing suitability orcompatibility, for example, with a filler is limited. In the applicationwhere physical properties such as adhesion to another material, printingsuitability or compatibility, for example, with a filler are required, acopolymer of an ethylene and a polar group-containing vinyl monomer,produced by a high-pressure radical polymerization process, has beenused by itself or as a composition with another resin. However, thepolar group-containing ethylene-based polymer produced by high-pressureradical polymerization can be only a low-modulus material and is pooralso in the mechanical properties, and its application particularly to afield requiring high strength is limited even when used as a compositionwith another resin as well as when used by itself.

Since the 1990s, polar group-containing comonomer copolymerization usinga late transition metal complex catalyst has been aggressively studied,and there are known, for example, an (α-diimine)palladium complexreported by Brookhart et al., a (salicylamidinato)nickel catalystreported by Grubbs et al., and a (phosphanylphenolato)nickel catalystcalled a SHOP catalyst. In use of such a catalyst, the polymerizationtemperature is set to be relatively low so as to suppress a frequentoccurrence of chain transfer, and the productivity of the copolymer aswell as its molecular weight are generally low (see, for example,Non-Patent Document 1).

In 2002, Pugh et al. have reported that when a phosphine sulfonateligand is combined with a palladium compound and used as a catalystcomponent, copolymerization even at a high temperature (80° C.) can beperformed (see, Patent Document 1 and Non-Patent Document 2), and thistechnique enables realizing high productivity and moreover, ensures arelatively high content of a (meth)acrylic ester as a comonomer.However, the molecular weight (Mw) of the copolymer obtained has anupper limit of about tens of thousands and therefore, industrialapplication of this copolymer is also limited.

The phosphine sulfonate ligand above is estimated to be a chelating orpotentially chelating ligand and has been reported, for example, tobecome a chelated metal complex by complexing with palladium (Non-PatentDocument 3). Also, it has been reported that a phosphine carboxylateligand having a —CO₂H group becomes a chelated metal complex bycomplexing with nickel (Non-Patent Document 4).

Nozaki et al. have reported that a (phosphine-sulfonato)palladium(methyl)lutidine complex is isolated as a catalytically active componentand this is useful as a catalyst (see, Patent Document 2 and Non-PatentDocument 3). In this case, the catalytic activity is greatly enhanced,but the molecular weight still remains low.

Ethylene polymerization and ethylene/1-hexene copolymerization eachusing the isolated (phosphine sulfonato)palladium (methyl)lutidinecomplex have been reported by Jordan et al. (Non-Patent Document 6). Thereport says that this catalyst does not absorb 1-hexene in the case ofpolymerization under an ethylene pressure (3 MPa) but copolymerizes aslight amount of hexene in the case of a low ethylene pressure (0.5MPa).

Goodall et al. have developed a phosphine sulfonate ligand having abiphenyl structure by improving the phosphine sulfonate ligand (see, forexample, Patent Documents 3 to 8 and Non-Patent Document 5). It isdisclosed that by using this ligand as a catalyst for thecopolymerization of an ethylene and an acrylic ester, a copolymer havinga molecular weight (Mw) of 100,000 or more can be produced. However,according to the evaluation by the present inventors, it has been foundthat the comonomer content disadvantageously decreases.

Accordingly, in the field of copolymerization of an ethylene and a vinylacetate as a polar group-containing vinyl monomer or a ((meth)acrylicacid)-based olefin, development of a polymerization catalyst capable ofsatisfying both high copolymerizability and high molecular weight (Mw)is being demanded.

On the other hand, a ternary copolymer of an ethylene, an α-olefin and apolar group-containing monomer is also known and, for example, anethylene•1-octene•ethyl acrylate ternary copolymer having an ethylacrylate content of 12.1 to 35.5 mol % and being produced using aspecific chromium-based catalyst is disclosed in Patent Document 9.However, this polymer is yet insufficient in view of improving thebalance between the mechanical properties and the adhesion and moreover,it still leaves problems such as many sticky components, generation ofdie lip build up at the molding, and film blocking. Also, PatentDocument 10 discloses an ethylene•propylene•methyl acrylate ternarycopolymer having a propylene content of 13.5 to 18.5 mol % and a methylacrylate content of 8 to 27.2 mol % and being produced using a specificvanadium-based catalyst, but the studies by the present inventors haverevealed that the strength of the polymer obtained is below the levelexpected of a polyethylene as a material. In this way, compared with anethylene-based (co)polymer containing no polar group, great reduction inthe mechanical properties of an ethylene-based copolymer containing apolar group is inevitable.

RELATED ART Patent Document

-   Patent Document 1: JP-T-2002-521534 (the term “JP-T” as used herein    means a published Japanese translation of a PCT patent application)-   Patent Document 2: JP-A-2007-46032 (the term “JP-A” as used herein    means an “unexamined published Japanese patent application”)-   Patent Document 3: JP-A-2007-63280-   Patent Document 4: JP-A-2007-77395-   Patent Document 5: JP-A-2007-117991-   Patent Document 6: JP-A-2008-214628-   Patent Document 7: JP-A-2007-214629-   Patent Document 8: JP-A-2007-214630-   Patent Document 9: JP-A-1-282204-   Patent Document 10: JP-A-2000-319332

Non-Patent Document

-   Non-Patent Document 1: S. Mecking et al., J. Am. Chem. Soc., 1998,    120, 888.-   Non-Patent Document 2: E. Drent et al., Chem. Commun., 2002, 744.-   Non-Patent Document 3: K. Nozaki et al., Dalton TRANSACTIONS, 2006,    25-   Non-Patent Document 4: W. Keim, Stud. Surf. Sci. Catal., 1986, 25,    201.-   Non-Patent Document 5: J. P. Claverie et al., Macromolecular Rapid    Communications, 2007, 28, 2033-2038-   Non-Patent Document 6: R. F. Jordan et al., Organometallics, 2007,    26, 6624-35.

SUMMARY OF THE INVENTION Problems that the Invention is to Solve

Under these circumstances of the background art, the present inventionprovides an industrially useful α-olefin•((meth)acrylic acid)-basedcopolymer having both a high molecular weight and a high comonomercontent, a catalyst component capable of realizing the production of twodifferent kinds of α-olefin•((meth)acrylic acid)-based copolymers, and aproduction process of the copolymer using the catalyst.

Also, the present invention provides an α-olefin•((meth)acrylicacid)-based ternary copolymer having a very narrow molecular weightdistribution in a specific range and having a melting point in aspecific range.

Means for Solving the Problems

In order to solve the above-described problems, the present inventorshave intended to develop a polymerization catalyst capable of realizingthe production of an α-olefin•((meth)acrylic acid)-based olefincopolymer having both a high molecular weight an a high comonomercontent and have made various investigations of a ligand compound in alate transition metal complex catalyst, as a result, it has been foundthat novel triarylphosphine and triarylarsine compounds remarkablyfunction as a polymerization catalyst component meeting theabove-described purpose. The present invention has been realized basedon this finding.

These triarylphosphine and triarylarsine compounds having a specificstructure are a novel compound constituting a first invention of thepresent invention, that is, a triarylphosphine or triarylarsine compoundrepresented by the following formula (1). (Incidentally, the term “thepresent invention” means the invention group consisting of respectiveinvention units of the following first to twentieth inventions.)

(wherein Y is phosphorus or arsenic, Z is —SO₃H or CO₂H, each of R¹ toR⁴ independently represents a hydrogen atom, a hydrocarbon group havinga carbon number of 1 to 30, a halogen atom-substituted hydrocarbon grouphaving a carbon number of 1 to 30, a heteroatom-containing hydrocarbongroup having a carbon number of 1 to 30, an alkoxy group having a carbonnumber of 1 to 30, or an aryloxy group having a carbon number of 6 to30, at least one of R¹ to R⁴ is a substituent where the carbon directlybonded to the aromatic ring is single-bonded to two or more elementsselected from the group consisting of C, O and N, and each of R⁵ to R¹⁴independently represents a hydrogen atom, a halogen atom, a hydrocarbongroup having a carbon number of 1 to 30, a halogen atom-substitutedhydrocarbon group having a carbon number of 1 to 30, aheteroatom-containing hydrocarbon group having a carbon number of 1 to30, an alkoxy group having a carbon number of 1 to 30, an aryloxy grouphaving a carbon number of 6 to 30, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 30).

As a second invention, the present invention provides the noveltriarylphosphine or triarylarsine compound, wherein in formula (1), eachof R¹ to R⁴ independently represents a hydrogen atom, a hydrocarbongroup having a carbon number of 1 to 30, a halogen atom-substitutedhydrocarbon group having a carbon number of 1 to 30, aheteroatom-containing hydrocarbon group having a carbon number of 1 to30, an alkoxy group having a carbon number of 1 to 30, or an aryloxygroup having a carbon number of 6 to 30 and at least one of R¹ to R⁴ isa secondary or tertiary alkyl group.

As a third invention, the present invention provides a noveltriarylphosphine or triarylarsine compound represented by the followingformula (1):

(wherein Y is phosphorus or arsenic, Z is —SO₃H or CO₂H, each of R¹ toR⁴ independently represents a hydrogen atom or a hydrocarbon grouphaving a carbon number of 1 to 30, which may have a heteroatom, at leastone of R¹ to R⁴ is a secondary or tertiary alkyl group, and each of R⁵to R¹⁴ independently represents a hydrogen atom, a halogen atom, or ahydrocarbon group having a carbon number of 1 to 30, which may have aheteroatom).

As a fourth invention, the present invention provides the noveltriarylphosphine or triarylarsine compound, wherein in formula (1) atleast one of R¹ and R² and at least one of R³ and R⁴ are a secondary ortertiary alkyl group.

As a fifth invention, the present invention provides an α-olefinpolymerization catalyst obtained by reacting the compound above and aGroup 8-10 transition metal compound.

As a sixth invention, the present invention provides an α-olefinpolymerization catalyst comprising the compound above, a Group 8-10transition metal compound and a fine particle support.

As a seventh invention, the present invention provides a metal complexrepresented by the following formula (2):

(wherein Y is phosphorus or arsenic, Z is —SO₃— or CO₂—, each of R¹ toR⁴ independently represents a hydrogen atom, a hydrocarbon group havinga carbon number of 1 to 30, a halogen atom-substituted hydrocarbon grouphaving a carbon number of 1 to 30, a heteroatom-containing hydrocarbongroup having a carbon number of 1 to 30, an alkoxy group having a carbonnumber of 1 to 30, or an aryloxy group having a carbon number of 6 to30, at least one of R¹ to R⁴ is a substituent where the carbon directlybonded to the aromatic ring is single-bonded to two or more elementsselected from the group consisting of C, O and N, each of R⁵ to R¹⁴independently represents a hydrogen atom, a halogen atom, a hydrocarbongroup having a carbon number of 1 to 30, a halogen atom-substitutedhydrocarbon group having a carbon number of 1 to 30, aheteroatom-containing hydrocarbon group having a carbon number of 1 to30, an alkoxy group having a carbon number of 1 to 30, an aryloxy grouphaving a carbon number of 6 to 30, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 30, M represents ametal atom selected from the group consisting of transition metals ofGroups 8 to 10, A represents a hydrogen atom, a halogen atom, an alkylgroup having a carbon number of 1 to 30, which may have a heteroatom, oran aryl group having a carbon number of 6 to 30, which may have aheteroatom, B represents an arbitrary ligand coordinated to M, and A andB may combine with each other to form a ring).

As an eighth invention, the present invention provides the metalcomplex, wherein in formula (2), each of R¹ to R⁴ independentlyrepresents a hydrogen atom, a hydrocarbon group having a carbon numberof 1 to 30, a halogen atom-substituted hydrocarbon group having a carbonnumber of 1 to 30, a heteroatom-containing hydrocarbon group having acarbon number of 1 to 30, an alkoxy group having a carbon number of 1 to30, or an aryloxy group having a carbon number of 6 to 30, and at leastone of R¹ to R⁴ is a secondary or tertiary alkyl group.

As a ninth invention, the present invention provides a metal complexrepresented by the following formula (2):

(wherein Y is phosphorus or arsenic, Z is —SO₃— or CO₂—, each of R¹ toR⁴ independently represents a hydrogen atom or a hydrocarbon grouphaving a carbon number of 1 to 30, which may have a heteroatom, at leastone of R¹ to R⁴ is a secondary or tertiary alkyl group, each of R⁵ toR¹⁴ independently represents a hydrogen atom, a halogen atom, or ahydrocarbon group having a carbon number of 1 to 30, which may have aheteroatom, M represents a metal atom selected from the group consistingof transition metals of Groups 8 to 10, A represents a hydrogen atom, analkyl group having a carbon number of 1 to 30, which may have aheteroatom, or an aryl group having a carbon number of 6 to 30, whichmay have a heteroatom, B represents an arbitrary ligand coordinated toM, and A and B may combine with each other to form a ring).

As a tenth invention, the present invention provides the metal complex,wherein in formula (2), at least one of R¹ and R² and at least one of R³and R⁴ are a secondary or tertiary alkyl group.

As an eleventh invention, the present invention provides an α-olefinpolymerization catalyst comprising the metal complex above.

As a twelfth invention, the present invention provides an α-olefinpolymerization catalyst comprising the metal complex above and a fineparticle support.

As a thirteenth invention, the present invention provides the α-olefinpolymerization catalyst, wherein the fine particle support is anion-exchanging layered silicate.

As a fourteenth invention, the present invention provides the α-olefinpolymerization catalyst, wherein the ion-exchanging layered silicatebelongs to a smectite group.

As a fifteenth invention, the present invention provides a process forproducing an α-olefin•((meth)acrylic acid)-based copolymer, comprisingcopolymerizing an α-olefin and a (meth)acrylic acid or ester in thepresence of the α-olefin polymerization catalyst above.

As a sixteenth invention, the present invention provides a process forproducing an α-olefin•((meth)acrylic acid)-based copolymer, comprisingcopolymerizing three components: two different kinds of α-olefins; and a(meth)acrylic acid or ester, in the presence of the α-olefinpolymerization catalyst above.

As a seventeenth invention, the present invention provides a ternarycopolymer of an ethylene, an α-olefin having a carbon number of 3 to 10and a (meth)acrylic acid or ester represented by CH₂═C(R¹⁸)CO₂(R¹⁹)(wherein R¹⁸ is a hydrogen atom or an alkyl group having a carbon numberof 1 to 10, and R¹⁹ is a hydrogen atom or an alkyl group having a carbonnumber of 1 to 30, which may contain a hydroxyl group, an alkoxy groupor an epoxy group on an arbitrary position), the ternary copolymersatisfying the following requirements (a) and (b):

(a) the ratio Mw/Mn of the weight average molecular weight (Mw) to thenumber average molecular weight (Mn) satisfies the followingrelationship:1.5≦Mw/Mn≦3

(b) the melting point Tm (° C.), the α-olefin content [C] (mol %) andthe polar group-containing vinyl monomer content [X] (mol %) satisfy thefollowing relationship:60≦Tm≦135−6.4×([C]+[X])wherein Tm is a peak temperature of a melting curve obtained by themeasurement using a differential scanning calorimeter (DSC) and when aplurality of melting peaks are detected, Tm is the temperature of themaximum peak out of detected peaks.

As an eighteenth invention, the present invention provides the ternarycopolymer above, wherein a phase angle δ(G*=0.1 MPa) at G*=0.1 MPa asmeasured by a rotary rheometer is from 40 to 75°.

As a nineteenth invention, the present invention provides the ternarycopolymer above, wherein a difference T90−T10 (° C.) between atemperature T10 (° C.) allowing 10 wt % of the total to elute in anintegrated elution curve as determined by a continuous temperaturerising elution fractionation method (TREF) and a temperature T90 (° C.)allowing 90 wt % of the total to elute, and a weight average elutiontemperature Tw (° C.) satisfy the following relationship:28−0.3×Tw≦T90−T10 41−0.3×Tw

As a twentieth invention, the present invention provides the ternarycopolymer above, wherein the carbon number of the α-olefin is any of 4to 8.

Advantage of the Invention

Copolymerization of an α-olefin and a ((meth)acrylic acid)-based olefinis performed in the presence of a polymerization catalyst according tothe present invention, whereby an industrially usefulα-olefin•((meth)acrylic acid)-based olefin copolymer having both a highmolecular weight and a high comonomer content can be produced.Incidentally, this remarkable effect is verified by the data in thelater-described Examples of the present invention and the comparison ofExamples with Comparative Examples.

A catalyst component is supported on a fine particle support, wherebythe properties of the produced polymer can be improved. In turn,particularly, the adaptability to a polymer production process requiringpolymer particulation, such as slurry polymerization or vapor phasepolymerization, can be improved.

This olefin copolymer is excellent in mechanical and thermal propertiesand applicable as a useful formed body. More specifically, the copolymerof the present invention can be applied to various uses such as film,sheet, adhesive resin, binder and compatibilizer, by utilizing its goodproperties in terms of, for example, coatability, printability,antistatic property, inorganic filler dispersibility, adhesion to otherresins, and compatibilizing ability for other resins.

MODE FOR CARRYING OUT THE INVENTION

The present invention relates to novel triarylphosphine andtriarylarsine compounds having a specific structure, a catalyst wheresuch a novel compound is coordinated to a specific metal element, anα-olefin•((meth)acrylic acid)-based olefin copolymer using them, and aproduction process for two different kinds of α-olefin•((meth)acrylicacid)-based olefin copolymers.

Those novel compounds, the polymerization catalyst, the constituentcomponents (monomer components) of the polymer, the production(polymerization) process, and the like are described in detail below.

1. Triarylphosphine and Triarylarsine Compounds

In the polymerization catalyst of the present invention, a noveltriarylphosphine or triarylarsine compound working out to a ligand to aspecific metal element is represented by the following formula (1):

(wherein Y is phosphorus or arsenic, Z is —SO₃H or CO₂H, each of R¹ toR⁴ independently represents a hydrogen atom, a hydrocarbon group havinga carbon number of 1 to 30, a halogen atom-substituted hydrocarbon grouphaving a carbon number of 1 to 30, a heteroatom-containing hydrocarbongroup having a carbon number of 1 to 30, an alkoxy group having a carbonnumber of 1 to 30, or an aryloxy group having a carbon number of 6 to30, at least one of R¹ to R⁴ is a substituent where the carbon directlybonded to the aromatic ring is single-bonded to two or more elementsselected from the group consisting of C, O and N, and each of R⁵ to R¹⁴independently represents a hydrogen atom, a halogen atom, a hydrocarbongroup having a carbon number of 1 to 30, a halogen atom-substitutedhydrocarbon group having a carbon number of 1 to 30, aheteroatom-containing hydrocarbon group having a carbon number of 1 to30, an alkoxy group having a carbon number of 1 to 30, an aryloxy grouphaving a carbon number of 6 to 30, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 30).

Y is phosphorus or arsenic, preferably phosphorus. Z is —SO₃H or CO₂H,preferably —SO₃H.

Each of R¹ to R⁴ independently represents a hydrogen atom, a hydrocarbongroup having a carbon number of 1 to 30, a halogen atom-substitutedhydrocarbon group having a carbon number of 1 to 30, aheteroatom-containing hydrocarbon group having a carbon number of 1 to30, an alkoxy group having a carbon number of 1 to 30, or an aryloxygroup having a carbon number of 6 to 30, and at least one of R¹ to R⁴ isa substituent where the carbon directly bonded to the aromatic ring issingle-bonded to two or more elements selected from the group consistingof C, O and N. R¹ to R⁴ are in the ortho-position with respect to thecentral Group 15 element (phosphorus or arsenic), that is, thetriarylphosphine compound of the present invention has at least onesterically bulky substituent in the molecule (in the ortho-position),which is one of the characteristic features. Accordingly, at least oneof R¹ and R² and at least one of R³ and R⁴ are preferably a substituentwhere the carbon directly bonded to the aromatic ring is single-bondedto two or more elements selected from the group consisting of C, O andN.

The substituent where the carbon directly bonded to the aromatic ring issingle-bonded to two or more elements selected from the group consistingof C, O and N includes a secondary or tertiary alkyl group composed oftwo or more carbons C, an alkoxyalkyl group or cyclic ethers composed ofone carbon C and one oxygen O, pyrrolidines or pyrroles composed of onecarbon C and one nitrogen N, acetals composed of two oxygens O,morpholines or oxazoles composed of one oxygen O and one nitrogen N, andimidazolidines or imidazoles composed of two nitrogens N. Thesubstituents containing two or more C, O or N may combine to form aring. Among these, a secondary or tertiary alkyl group, an alkoxyalkylgroup and cyclic ethers are preferred, and the later-described secondaryor tertiary alkyl group and a tetrahydrofuryl group are more preferred.

The secondary or tertiary alkyl group means a group where the elementdirectly bonded to the phenyl group is carbon and the site thereof is asecondary or tertiary alkyl group. Each of R¹ to R⁴ which are asecondary or tertiary alkyl group is independently a hydrocarbon grouphaving a carbon number of 3 to 30, which may contain a heteroatom.

Each of R¹ to R⁴ when these are a secondary or tertiary alkyl group isindependently a hydrocarbon group having a carbon number of 3 to 30,preferably a hydrocarbon group having a carbon number of 3 to 12, whichis a secondary alkyl group, and more preferably a hydrocarbon grouphaving a carbon number of 3 to 6. Specific preferred examples thereofinclude tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethyl group,isopropyl group, 1,1-dimethylpropyl group, 1,1,2-trimethylpropyl group,1,1-diethylpropyl group, 1-phenyl-2-propyl group, tertiary butyl group,isobutyl group, 1,1-dimethylbutyl group, 2-isopentyl group, 3-isopentylgroup, 2-isohexyl group, 3-isohexyl group, 2-ethylhexyl group,2-isoheptyl group, 3-isoheptyl group, 4-isoheptyl group, 2-propylheptylgroup, 2-isooctyl group, 3-isononyl group, 1-adamantyl group,cyclopropyl group, cyclobutyl group, cyclopentyl group,methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group,cycloheptyl group, cyclooctyl group, cyclododecyl group, exo-norbornylgroup, endo-norbornyl group, 2-bicyclo[2.2.2]octyl group, 2-adamantylgroup, nopinyl group, menthyl group, neomenthyl group and neopentylgroup. Among these, isopropyl group, isobutyl group and cyclohexyl groupare more preferred.

Each of R¹ to R⁴ which are a secondary or tertiary alkyl group maycontain a heteroatom in its partial structure. Introduction of anelectron-donating group ascribable to the heteroatom can increase theelectron density of the central metal spatially adjacent thereto and iseffective for enhancing the catalytic activity. The heteroatomindicates, in a broad sense, a nonmetallic atom except for carbon atom,hydrogen atom and atoms of Groups 17 and 18 but is preferably a second-or third-row nonmetallic atom, more preferably an oxygen atom or anitrogen atom, still more preferably an oxygen atom.

Each of these heteroatom-containing secondary or tertiary alkyl groupsis independently an oxygen atom-containing secondary alkyl group havinga carbon number of 4 to 30, preferably an oxygen atom-containingsecondary alkyl group having a carbon number of 4 to 15, more preferablyan oxygen atom-containing secondary alkyl group having a carbon numberof 4 to 7, still more preferably an oxygen atom-containing secondaryalkyl group having a carbon number of 4 to 7.

Specific preferred examples thereof include 1-(methoxymethyl)ethylgroup, 1-(ethoxymethyl)ethyl group, 1-(phenoxymethyl)ethyl group,1-(methoxyethyl)ethyl group, 1-(ethoxyethyl)ethyl group,1-(dimethylaminomethyl)ethyl group, 1-(diethylaminomethyl)ethyl group,di(methoxymethyl)methyl group, di(ethoxymethyl)methyl group anddi(phenoxymethyl)methyl group.

Each of R¹ to R⁴ when these are not a secondary or tertiary alkyl groupis independently a hydrogen atom, a hydrocarbon group having a carbonnumber of 1 to 30, a halogen atom-substituted hydroxyl group having acarbon number of 1 to 30, a heteroatom-containing hydrocarbon grouphaving a carbon number of 1 to 30, an alkoxy group having a carbonnumber of 1 to 30, or an aryloxy group having a carbon number of 6 to30.

The hydrocarbon group having a carbon number of 1 to 30 is preferably analkyl group having a carbon number of 1 to 6, and specific preferredexamples thereof include methyl group, ethyl group, normal-propyl group,n-butyl group and normal-hexyl group, with methyl group being morepreferred.

The halogen atom-substituted hydrocarbon group having a carbon number of1 to 30 is preferably an alkyl group having a carbon number of 1 to 6and being substituted with one halogen atom. The halogen atomsubstituted is preferably a fluorine atom, and specific preferredexamples thereof include fluoromethyl group, 1-fluoroethyl group,2-fluoroethyl group, 3-fluoropropyl group, 4-fluorobutyl group and6-fluorohexyl group.

The heteroatom-containing hydrocarbon group having a carbon number of 1to 30 is preferably an oxygen atom-containing hydrocarbon group having acarbon number of 1 to 4, and specific preferred examples thereof includemethoxymethyl group and ethoxymethyl group.

The alkoxy group having a carbon number of 1 to 30 is preferably analkoxy group having a carbon number of 1 to 6, and specific preferredexamples thereof include methoxy group and ethoxy group.

The aryloxy group having a carbon number of 6 to 30 is preferably anaryloxy group having a carbon number of 6 to 12, and specific preferredexamples thereof include phenoxy group and 2-methylphenoxy group.

Among these specific examples of the substituent group when R¹ to R⁴ arenot a secondary or tertiary alkyl group, a hydrogen atom and an alkylgroup having a carbon number of 1 to 6 are preferred, and a hydrogenatom and a methyl group are more preferred.

Each of R⁵ to R¹⁴ is independently a hydrogen atom, a halogen atom, ahydrocarbon group having a carbon number of 1 to 30, a halogenatom-substituted hydrocarbon group having a carbon number of 1 to 30, aheteroatom-containing hydrocarbon group having a carbon number of 1 to30, an alkoxy group having a carbon number of 1 to 30, an aryloxy grouphaving a carbon number of 6 to 30, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 30.

These substituents are a substituent at a site kept relatively distantfrom the central metal during complex formation and therefore, may besufficient if it is a substituent not adversely affecting the formationof the phosphorus-sulfonic acid ligand complex. The electronic effect ofthese substituents is considered to affect the catalytic performancecompared with their steric effect, and an electron-donating substituentis preferred. The substituents above may be the same or different.

Examples of the halogen atom include fluorine, chlorine and bromine.

Examples of the hydrocarbon group having a carbon number of 1 to 30include an alkyl group, a cycloalkyl group, an alkenyl group and an arylgroup.

Examples of the alkyl group and cycloalkyl group include methyl group,ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexylgroup, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group,tert-butyl group, tricyclohexylmethyl group, 1,1-dimethyl-2-phenylethylgroup, isopropyl group, 1-dimethylpropyl group, 1,1,2-trimethylpropylgroup, 1,1-diethylpropyl group, 1-phenyl-2-propyl group, isobutyl group,1,1-dimethylbutyl group, 2-pentyl group, 3-pentyl group, 2-hexyl group,3-hexyl group, 2-ethylhexyl group, 2-heptyl group, 3-heptyl group,4-heptyl group, 2-propylheptyl group, 2-octyl group, 3-nonyl group,cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopropylgroup, methylcyclopentyl group, cyclohexyl group, methylcyclohexylgroup, cycloheptyl group, cyclooctyl group, cyclododecyl group,1-adamantyl group, 2-adamantyl group, exo-norbomyl group, endo-norbomylgroup, 2-bicyclo[2,2,2]octyl group, nopinyl group, decahydronaphthylgroup, menthyl group, neomenthyl group, neopentyl group and 5-decylgroup. Among these substituents, isopropyl group, isobutyl group andcyclohexyl group are preferred.

The alkenyl group includes vinyl group, allyl group, butenyl group,cinnamyl group and styryl group.

The aryl group includes phenyl group, naphthyl group, anthracenyl groupand fluorenyl group. Examples of the substituent which can be present onthe aromatic ring of such an aryl group include an alkyl group, an arylgroup, a fused aryl group, a phenylcyclohexyl group, a phenylbutenylgroup, a tolyl group, a xylyl group, a p-ethylphenyl group and apentafluorophenyl group. Among these substituents, phenyl group andpentafluorophenyl group are preferred.

The halogen atom-substituted hydrocarbon group having a carbon number of1 to 30 is a substituent where the above-described hydrocarbon grouphaving a carbon number of 1 to 30 is substituted with a halogen atomsuch as fluorine, chlorine and bromine.

The heteroatom which may be contained in the heteroatom-containinghydrocarbon group having a carbon number of 1 to 30 is preferably anoxygen atom or a nitrogen atom. Specific examples of theheteroatom-containing hydrocarbon group having a carbon number of 1 to30 include OR¹⁵, CO₂R¹⁵, CO₂M′, C(O)N(R¹⁵)₂, C(O)R¹⁵, SO₂R¹⁵, SOR¹⁵,OSO₂R¹⁵, P(O)(OR¹⁵)_(2-y)(R¹⁶)_(y), CN, NHR¹⁵, N(R¹⁵)₂, NO₂, SO₃M′,PO₃M′₂, P(O)(OR¹⁵)₂M′, and a hydrocarbon group having a substituentcontaining a heteroatom, such as epoxy group. Here, M′ represents analkali metal, an alkaline earth metal, an ammonium, a quaternaryammonium or a phosphonium, x represents an integer of 0 to 3, yrepresents an integer of 0 to 2, R¹⁵ represents hydrogen or ahydrocarbon group having a carbon number of 1 to 20, and R¹⁶ representsa hydrocarbon group having a carbon number of 1 to 20. Among theseheteroatom-containing substituents, OR¹⁵ and N(R¹⁵)₂ are preferred, andOR¹⁵ is more preferred.

The alkoxy group having a carbon number of 1 to 30 is preferably analkoxy group having a carbon number of 1 to 6, and specific preferredexamples include methoxy group and ethoxy group.

The aryloxy group having a carbon number of 6 to 30 is preferably anaryloxy group having a carbon number of 6 to 12, and specific preferredexamples thereof include phenoxy group and 2-methylphenoxy group.

The silyl group substituted with a hydrocarbon group having a carbonnumber of 1 to 30 is preferably a silyl group having a carbon number of3 to 18, and specific preferred examples thereof include trimethylsilylgroup, dimethylphenylsilyl group, diphenylmethylphenylsilyl group andtriphenylsilyl group.

The ligand of the present invention is estimated to be a chelating orpotentially chelating ligand. For example, it has been reported that aligand having an —SO₃H group becomes a chelated metal complex bycomplexing with palladium (Non-Patent Document 3) and a ligand having a—CO₂H group becomes a chelated metal complex by complexing with nickel(Non-Patent Document 4).

2. Synthesis of Triarylphosphine or Triarylarsine Compound

Synthesis of the triarylphosphine compound as the first invention isperformed through the following route. That is, some synthesis routesare known for the compound, and specific examples thereof include aroute where a lithio form of an aryl group (aryl lithium salt) to beintroduced is reacted with the raw material phosphorus trichloride in anappropriate molar ratio. After the reaction, extraction under acidicconditions and washing follow, whereby the target product can beobtained. Synthesis of the triarylarsine compound is performed in thesame manner.

3. Synthesis of Polymerization Catalyst

The polymerization catalyst of the present invention is an α-olefinpolymerization catalyst obtained by reacting the novel triarylphosphineor triarylarsine compound represented by formula (1) and a Group 8-10transition metal compound.

Synthesis of the catalyst composition is generally performed by bringinga Group 8-10 transition metal compound into contact with the ligand in asolution or a slurry. The transition metal compound is preferably aGroup 10 transition metal compound, and the synthesis is performedusing, for example, bis(dibenzylideneacetone)palladium,tetrakis(triphenylphosphine)palladium, palladium sulfate, palladiumacetate, bis(allylpalladium chloride), palladium chloride, palladiumbromide, (cyclooctanediene)palladium (methyl) chloride, dimethyl(tetramethylethylenediamine)palladium, bis(cyclooctadiene)nickel, nickelchloride, nickel bromide, (tetramethylethylenediamine)nickel(methyl)chloride, dimethyl (tetramethylethylenediamine)nickel or(cyclooctadiene)nickel (methyl)chloride.

The complexing reaction may be performed in a reaction vessel for use inthe copolymerization with an α-olefin or may be performed in a separatevessel different from the reaction vessel. After the complex formation,the metal complex may be isolated by extraction and used for a catalystor may be used for a catalyst without isolation. It is also possible toperform the reaction in the presence of the later-described poroussupport. Furthermore, as for the catalyst composition of the presentinvention, one kind of a catalyst composition may be used alone, or aplurality of kinds of catalyst compositions may be used in combination.In particular, the combination use of a plurality of kinds of catalystcompositions is useful for the purpose of broadening the molecularweight distribution or the comonomer content distribution.

The metal complex obtained by reacting a triarylphosphine ortriarylarsine compound represented by formula (1) and a Group 8-10transition metal compound may be a metal complex represented by thefollowing formula (2):

(wherein Y is phosphorus or arsenic, Z is —SO₃— or CO₂—, each of R¹ toR⁴ independently represents a hydrogen atom, a hydrocarbon group havinga carbon number of 1 to 30, a halogen atom-substituted hydrocarbon grouphaving a carbon number of 1 to 30, a heteroatom-containing hydrocarbongroup having a carbon number of 1 to 30, an alkoxy group having a carbonnumber of 1 to 30, or an aryloxy group having a carbon number of 6 to30, at least one of R¹ to R⁴ is a substituent where the carbon directlybonded to the aromatic ring is single-bonded to two or more elementsselected from the group consisting of C, O and N, each of R⁵ to R¹⁴independently represents a hydrogen atom, a halogen atom, a hydrocarbongroup having a carbon number of 1 to 30, a halogen atom-substitutedhydrocarbon group having a carbon number of 1 to 30, aheteroatom-containing hydrocarbon group having a carbon number of 1 to30, an alkoxy group having a carbon number of 1 to 30, an aryloxy grouphaving a carbon number of 6 to 30, or a silyl group substituted with ahydrocarbon group having a carbon number of 1 to 30, M represents ametal atom selected from the group consisting of transition metals ofGroups 8 to 10, A represents a hydrogen atom, a halogen atom, an alkylgroup having a carbon number of 1 to 30, which may have a heteroatom, oran aryl group having a carbon number of 6 to 30, which may have aheteroatom, B represents an arbitrary ligand coordinated to M, and A andB may combine with each other to form a ring).

Here, Y, Z and R¹ to R¹⁴ are the same as the substituents in thetriarylphosphine or triarylarsine compound represented by formula (1).

M represents a Group 8-10 transition metal and is preferably Fe, Co, Ni,Pd, Pt or lanthanide, more preferably Ni or Pd.

A represents a hydrogen atom, a halogen atom, an alkyl group having acarbon number of 1 to 30, which may have a heteroatom, or an aryl grouphaving a carbon number of 6 to 30, which may have a heteroatom. Theheteroatom is preferably an oxygen atom, a nitrogen atom or a siliconatom, more preferably an oxygen atom.

The alkyl group is preferably an alkyl group having a carbon number of 1to 6, and examples thereof include a methyl group, an ethyl group, atrifluoromethyl group, an acyl group and an acetoxy group. The arylgroup is preferably an aryl group having a carbon number of 6 to 13, andexamples thereof include a phenyl group, a tolyl group, a xylyl group, aphenacyl group and a pentafluorophenyl group. Among these substituents,a hydrogen atom, a methyl group and a phenyl group are preferred.

B is an arbitrary ligand coordinated to M. This ligand is a hydrocarboncompound having a carbon number of 1 to 20 and containing oxygen,nitrogen, phosphorus or sulfur as an atom capable of coordinationbonding. Specific examples of the ligand include phosphines, pyridinederivatives, piperidine derivatives, alkyl ether derivatives, aryl etherderivatives, alkylaryl ether derivatives, ketones, cyclic ethers,alkylnitrile derivatives, arylnitrile derivatives, alcohols, amides,aliphatic esters, aromatic esters and amines. Preferred ligands areketones, cyclic ethers, phosphines and pyridine derivatives, and morepreferred ligands are acetone, tetrahydrofuran, pyridine, lutidine andtriphenylphosphine.

4. Fine Particle Support

As for the fine particle support used in the present invention, anarbitrary fine particle support can be used as long as the purport ofthe present invention is not impaired.

In general, an inorganic oxide or a polymer support can be suitablyused. Specific examples thereof include SiO₂, Al₂O₃, MgO, ZrO₂, TiO₂,B₂O₃, CaO, ZnO, BaO, ThO₂ and a mixture thereof. A mixed oxide such asSiO₂—Al₂O₃, SiO₂—V₂O₅, SiO₂—TiO₂, SiO₂—MgO and SiO₂—Cr₂O₃ can be alsoused, and an inorganic silicate, a polyethylene support, a polypropylenesupport, a polystyrene support, a polyacrylic acid support, apolymethacrylic acid support, a polyacrylic ester support, a polyestersupport, a polyamide support, a polyimide support and the like can beused. Among these supports, a support composed of an inorganic oxide ispreferred, an ion-exchanging layered silicate is more preferred. Stillmore preferably, the smectite group is used.

Examples of the ion-exchanging layered silicate which can be usedinclude clay, clay mineral, zeolite and diatomaceous earth. For thesematerials, a synthesized product may be used or a naturally occurringmineral may be used.

Specific examples of the clay and clay mineral include the allophanefamily such as allophane; the kaolin family such as dickite, nacrite,kaolinite and anauxite; the halloysite family such as metahalloysite andhalloysite; the serpentine family such as chrysotile, lizardite andantigorite; the smectite family such as montmorillonite, sauconite,beidellite, nontronite, saponite and hectorite; the vermiculite familysuch as vermiculite; a mica mineral such as illite, sericite andglauconite; attapulgite; sepiolite; palygorskite; bentonite; kibushiclay; gairome clay; hisingerite; pyrophyllite; and a group of chlorites.These may form a mixed layer.

Examples of the artificially synthesized product include a syntheticmica, a synthetic hectorite, a synthetic saponite and a synthetictaeniolite.

Among these specific examples, preferred are the kaolin family such asdickite, nacrite, kaolinite and anauxite, the halloysite family such asmetahalloysite and halloysite, the serpentinite family such aschrysotile, rizaldite and antigorite, the smectite family such asmontmorillonite, sauconite, beidellite, nontronite, saponite andhectorite, a vermiculite mineral such as vermiculite, a mica mineralsuch as illite, sericite and glauconite, a synthetic mica, a synthetichectorite, a synthetic saponite and a synthetic taeniolite, and morepreferred are the smectite family such as montmorillonite, sauconite,beidellite, nontronite, saponite and hectorite, a vermiculite mineralsuch as vermiculite, a synthetic mica, a synthetic hectorite, asynthetic saponite and a synthetic taeniolite.

Such a fine particle support may be used directly or may be subjected toan acid treatment with hydrochloric acid, nitric acid, sulfuric acid orthe like and/or a treatment with salts such as LiCl, NaCl, KCl, CaCl₂,MgCl₂, Li₂SO₄, MgSO₄, ZnSO₄, Ti(SO₄)₂, Zr(SO₄)₂ and Al₂(SO₄)₃. In thetreatment, corresponding acid and base may be mixed to produce a salt inthe reaction system, thereby effecting the treatment, or a shape controlsuch as pulverization or granulation or a drying treatment may beperformed.

The fine particle support is not particularly limited in its particlediameter and the like, and an arbitrary fine particle may be used, butthe particle diameter in terms of the average particle diameter ispreferably from 5 to 200 μm, more preferably from 10 to 100 μm.

The fine particle support may be treated with an organic aluminumcompound before use. The organic aluminum compound used here has asubstituent selected from an alkyl group having a carbon number of 1 to20, a halogen, hydrogen, an alkoxy group and an amino group. Among thesesubstituents, an alkyl group having a carbon number of 1 to 20, hydrogenand an alkoxy group having a carbon number of 1 to 20 are preferred, andan alkyl group having a carbon number of 1 to 20 is more preferred. Whena plurality of substituents are present, they may be the same ordifferent. As for the organic aluminum compound, one kind of a compoundmay be used alone, or a plurality of kinds of compounds may be used incombination.

Specific examples of the organic aluminum compound includetrimethylaluminum, triethylaluminum, tri-normal-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-normal-hexylaluminum,tri-normal-octylaluminum, tri-normal-decylaluminum, diethylaluminumchloride, diethylaluminum sesquichloride, diethylaluminum hydride,diethylaluminum ethoxide, diethylaluminum dimethylamide,diisobutylaluminum hydride and diisobutylaluminum chloride. Among these,preferred are a trialkylaluminum and an alkylaluminum hydride, and morepreferred is a trialkylaluminum having a carbon number of 1 to 8.

5. Use Mode of Polymerization Catalyst

(1) Contact of Catalyst Components

The triarylphosphine or triarylarsine compound, the Group 8-10transition metal compound and the fine particle support can be contactedin an arbitrary order. In contacting the components, each component maybe contacted in the form of a solid or may be formed into a solventslurry or a uniform solution and then contacted. Examples of the orderof contacting respective components include:

contact order 1: The triarylphosphine or triarylarsine compound and theGroup 8-10 transition metal compound are contacted and then contactedwith the fine particle support;

contact order 2: The triarylphosphine or triarylarsine compound and thefine particle support are contacted and then contacted with the Group8-10 transition metal compound; and

contact order 3: The Group 8-10 transition metal compound and the fineparticle support are contacted and then contacted with thetriarylphosphine or triarylarsine compound.

Among these contacting methods, the contact order 1 is preferred. Also,after contacting the fine particle support with other catalystcomponents, the support may be washed with a solvent having noreactivity with the catalyst components. The solvent is preferably ahydrocarbon solvent or a halogenated hydrocarbon.

The triarylphosphine or triarylarsine compound is used in an amount ofusually from 0.001 to 10 mmol, preferably from 0.001 to 1 mmol, per 1 gof the fine particle support.

As for the temperature at which respective components are contacted, thecontact may be performed at an arbitrary temperature as long as it isnot more than the boiling point of the solvent, but the temperature ispreferably from room temperature to the boiling point of the solvent.

The contacted catalyst components may be used directly forpolymerization evaluation or may be dried to a solid state and stored.Furthermore, preliminary polymerization described below may be alsoperformed.

(2) Preliminary Polymerization

The contacted catalyst components may be subjected to preliminarypolymerization in the presence of an olefin by contacting the componentsinside or outside the polymerization tank. The olefin indicates ahydrocarbon containing at least one carbon-carbon double bond, andexamples thereof include ethylene, propylene, 1-butene, 1-hexene,3-methylbutene-1, styrene and divinylbenzene. However, the kind of theolefin is not particularly limited, and a mixture of such a hydrocarbonwith another olefin may be also used. An olefin having a carbon numberof 2 or 3 is preferred. The method for supplying the olefin may be anarbitrary method, for example, may be a method of supplying the olefinto the reaction tank at a constant rate or in a manner to keep theconstant pressure state, a method of combining these methods, or amethod of stepwise changing the rate or pressure.

6. Monomers Used

The monomers used in the production of the copolymer include anα-olefin, a ((meth)acrylic acid)-based olefin and other olefins, whichare described below.

(a) α-Olefin

One of the monomers for use in the present invention is an α-olefinrepresented by the formula: CH₂═CHR¹⁷ (hereinafter sometimes referred toas a “component (a)”). Here, R¹⁷ is hydrogen or an alkyl group having acarbon number of 1 to 20.

The component (a) is preferably an α-olefin with R¹⁷ having a carbonnumber of 1 to 10. The component (a) is more preferably ethylene,propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene,3-methyl-1-butene or 4-methyl-1-pentene, still more preferablypropylene, 1-butene, 1-pentene, 1-hexane or 1-octane, yet still morepreferably 1-hexene. Incidentally, one component (a) may be used alone,or a plurality of components (a) may be used in combination.

(b) ((Meth)Acrylic Acid)-Based Olefin

Another of the monomers for use in the present invention is a(meth)acrylic acid or a (meth)acrylic ester represented by the formula:CH₂═C(R¹⁸)CO₂(R¹⁹) (hereinafter, these are sometimes collectivelyreferred to as a “component (b)” or a “(meth)acrylic acid (or ester)”).Here, R¹⁸ is hydrogen or a hydrocarbon group having a carbon number of 1to 10 and my have a branch, a ring and/or an unsaturated bond, R¹⁹ ishydrogen or an alkyl group having a carbon number of 1 to 30, and R¹⁹may contain a heteroatom in an arbitrary position.

The component (b) is preferably a (meth)acrylic ester with R¹⁸ having acarbon number of 1 to 5 or a (meth)acrylic acid. The component (b) ismore preferably a methacrylic ester with R¹⁸ being a methyl group, anacrylic ester with R¹⁸ being hydrogen, or a (meth)acrylic acid. Thecomponent (b) is still more preferably, for example, methyl acrylate,ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate,isobutyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate,cyclohexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonylacrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluylacrylate, benzyl acrylate, hydroxyethyl acrylate, glycidyl acrylate, oracrylic acid. One component (b) may be used alone, or a plurality ofcomponents (b) may be used in combination.

(c) Other Olefins

Still another of the monomers for use in the present invention is otherolefins (hereinafter sometimes referred to as a “component (c)”).

Preferred examples of the component (c) include a cyclic olefin monomersuch as cyclopentene, cyclohexene, norbornene and ethylidenenorbornene,and a styrene-based monomer such as p-methylstyrene. The skeletalstructure of such a monomer may contain a hydroxyl group, an alkoxidegroup, a carboxylic acid group, an ester group or an aldehyde group.

The norbornene-based olefin can be produced by a Diels-Alder reaction([4+2]cycloaddition) using cyclopentadiene. The dienophile used is, forexample, diethyl azodicarboxylate, aldehyde, maleic anhydride,dihydrofuran, vinylpyridine, an alkyl acrylate or the above-describedsubstituted olefin (see, T. L. Gilchrist, Heterocyclic Chemistry, Chap.4.3.3, 1985). These monomers can be represented by formulae (3a) to(3f), wherein R²⁰ is a hydrocarbon group having a carbon number of 1 to30 and may contain a branch, a ring or an unsaturated bond.

The monomer specified in the component (a) may be also a hydroxylgroup-containing monomer such as (3-buten)-1-ol, an ethergroup-containing monomer such as methyl vinyl ether, a carboxylic acidgroup-containing monomer such as acrylic acid, an ester group-containingmonomer such as methyl acrylate, or a monomer containing an aldehydegroup or the like, such as acrolein. In addition, a diene derivative, amaleic anhydride, a vinyl acetate or the like is also usable.

7. Copolymerization Reaction

In the present invention, the copolymerization reaction is preformed inthe presence or absence of a hydrocarbon solvent such as propane,n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane,methylcyclohexane, a liquid such as liquefied α-olefin, or a polarsolvent such as diethyl ether, ethylene glycol dimethyl ether,tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone,methyl ethyl ketone, formamide, acetonitrile, methanol, isopropylalcohol and ethylene glycol. Also, a mixture of liquid compoundsdescribed here may be used as the solvent. In the case of obtaining highpolymerization activity or a high molecular weight, a hydrocarbonsolvent described above is preferred.

In performing the copolymerization of the present invention, thecopolymerization may be performed in the presence or absence of knownadditives. The additive is preferably a radical polymerization inhibitoror an additive having an action of stabilizing the copolymer produced.Preferred examples of the additive include a quinone derivative and ahindered phenol derivative. Specific examples of the additive which canbe used include monomethyl ether hydroquinone, 2,6-di-tert-butyl4-methylphenol (BHT), a reaction product of trimethylaluminum and BHT,and a reaction product of tetravalent titanium, alkoxide and BHT. Also,an inorganic or organic filler may be used as the additive, and thepolymerization may be performed in the presence of such a filler.

In the present invention, the polymerization form is not particularlylimited and, for example, slurry polymerization where at least a part ofthe produced polymer becomes a slurry in a medium, bulk polymerizationwhere the liquefied monomer itself works as a medium, vapor phasepolymerization where the polymerization is performed in vaporizedmonomers, and high-pressure ionic polymerization where at least a partof the produced polymer dissolves in monomers liquefied at a hightemperature under a high pressure, is preferably employed.

The polymerization form may be any of batch polymerization, semi-batchpolymerization and continuous polymerization or may be livingpolymerization, or the polymerization may be also performed whileallowing chain transfer to occur in parallel. Furthermore, a chainshuttling reaction or coordinative chain transfer polymerization (CCTP)may be performed by using a so-called chain shuttling agent (CSA) incombination.

The unreacted monomer or medium is separated from the produced copolymerand may be recycled. At the recycle, such a monomer or medium may bepurified and then reused or may be reused without purification. For theseparation of the unreacted monomer and the medium from the producedcopolymer, a conventionally known method may be used. Examples of themethod which can be used include filtration, centrifugal separation,solvent extraction, and reprecipitation using a poor solvent.

The copolymerization temperature, copolymerization pressure andcopolymerization time are not particularly limited but usually, can beoptimally set in the following ranges by taking into consideration theproductivity and the processing ability.

That is, these can be selected from the ranges where thecopolymerization temperature is usually from −20° C. to 300° C.,preferably from 0 to 250° C., more preferably from 50 to 100° C., thecopolymerization pressure is preferably from 0.1 to 200 MPa, preferablyfrom 0.3 to 100 MPa, more preferably from 0.3 to 5 MPa, and thecopolymerization time is from 0.1 minutes to 6 hours, preferably from0.5 minutes to 5 hours, more preferably from 10 minutes to 4 hours.

In the present invention, the copolymerization is generally performed inan inert gas atmosphere. for example, a nitrogen, argon or carbondioxide atmosphere can be used, and a nitrogen atmosphere is preferablyused. A small amount of oxygen or air may be mixed.

The supply of the catalyst and monomers to the copolymerization reactoris also not particularly limited, and various supply methods may beemployed according to the purpose. For example, in the case of batchpolymerization, a technique of previously supplying predeterminedamounts of the monomers to the copolymerization reaction and supplyingthe catalyst thereto may be employed. In this case, an additionalmonomer or an additional catalyst may be supplied to thecopolymerization reactor. In the case of continuous polymerization, atechnique of continuously or intermittently supplying predeterminedamounts of the monomers and the catalyst to the copolymerization reactorto continuously perform the copolymerization reaction may be employed.

As for the control of the composition of the copolymer, a method ofsupplying a plurality of monomers to the reactor and changing the supplyratio, thereby controlling the composition, can be generally used. Inaddition, a method of controlling the copolymerization composition byutilizing the difference in the monomer reactivity ratio due todifference in the catalyst structure, or a method of controlling thecopolymerization composition by utilizing the polymerization temperaturedependency of the monomer reactivity ratio, may be used.

For the control of the molecular weight of the copolymer, aconventionally known method can be used. That is, examples of the methodinclude a method of controlling the molecular weight by controlling thepolymerization temperature, a method of controlling the molecular weightby controlling the monomer concentration, a method of controlling themolecular weight by using a chain transfer agent, and a method ofcontrolling the molecular weight by controlling the ligand structure inthe transition metal complex.

In the case of using a chain transfer agent, a conventionally knownchain transfer agent can be used. Examples of the chain transfer agentwhich can be used include hydrogen and a metal alkyl. In the case wherethe component (b) or (c) itself works as a kind of chain transfer agent,the molecular weight can be also adjusted by controlling theconcentration of the component (b) or (c) or the ratio to the component(a). In the case of adjusting the molecular weight by controlling theligand structure in the transition metal complex, there may be utilizeda tendency that the molecular weight is generally increased by disposinga bulky substituent around the metal M, by disposing anelectron-donating group such as aryl group and heteroatom-containingsubstituent in such a manner as to enable interaction with the metal M,or by introducing a heteroatom into R¹⁸ to R²⁰.

8. Ternary Copolymer of Ethylene-α Olefin-(Meth)Acrylic Acid (or Ester)

As described above, the α olefin polymerization catalyst of the presentinvention can polymerize a polar group-containing monomer such as(meth)acrylic acid (or ester), and in particular, a ternary copolymer ofethylene-α olefin-(meth)acrylic acid (or ester) produced using thecatalyst of the present invention has the following novel properties.

That is, the ternary copolymer of the present invention is a ternarycopolymer of an ethylene, an α-olefin having a carbon number of 3 to 10and a (meth)acrylic acid or ester represented by CH₂═C(R¹⁸)CO₂(R¹⁹)(wherein R¹⁸ is hydrogen or an alkyl group having a carbon number of 1to 10, and R¹⁹ is hydrogen or an alkyl group having a carbon number of 1to 30, which may contain a hydroxyl group, an alkoxy group or an epoxygroup on an arbitrary position), the ternary copolymer satisfying thefollowing requirements (a) and (b):

(a) the ratio Mw/Mn of the weight average molecular weight (Mw) to thenumber average molecular weight (Mn) satisfies the followingrelationship:1.5≦Mw/Mn≦3

(b) the melting point Tm (° C.), the α-olefin content [C] (mol %) andthe polar group-containing vinyl monomer content [X] (mol %) satisfy thefollowing relationship:60≦Tm≦135−6.4×([C]+[X])wherein Tm is the peak temperature of a melting curve obtained by themeasurement using a differential scanning calorimeter (DSC) and when aplurality of melting peaks are detected, Tm is the temperature of themaximum peak out of detected peaks.

Mw/Mn of the copolymer of the present invention must be 3.0 or less, andMw/Mn is preferably 2.7 or less, more preferably 2.4 or less. If Mw/Mnexceeds 3, the mechanical strength, particularly the impact strength,decreases.

Mw/Mn of the copolymer of the present invention is 1.5 or more. It isdifficult to industrially produce a copolymer having Mw/Mn of less than1.5.

In the ternary copolymer of the present invention, the melting point Tm(° C.), the α-olefin content [C] (mol %) and the polar group-containingvinyl monomer content [X] (mol %) must satisfy the relationship of60≦Tm≦135−6.4×([C]+[X]). The melting point changes according to how theα-olefin and/or polar group-containing vinyl monomer copolymerized arearranged in the molecular chain. In the case where the α-olefin or thepolar group-containing monomer is unevenly distributed to, for example,the terminal of the molecular chain, the crystallizable ethylene chainbecomes long on average and this brings a high melting point even when([C]+[X]) is the same. On the other hand, in the case where the α-olefinor the polar group-containing monomer is uniformly distributed insidethe molecular chain, the melting point lowers. If the melting point isless than 60° C., the minimum heat resistance required of anethylene-based copolymer cannot be retained, whereas if the meltingpoint exceeds 135−6.4×([C]+[X]), the crystal lamella becomes thick andthe number of the molecules connecting a lamella and a lamella isdecreased, as a result, the mechanical properties such as impactstrength are impaired.

Also, for attaining the objects of the present invention, the phaseangle δ(G*=0.1 MPa) at G*=0.1 MPa as measured by a rotary rheometer ispreferably 40° or more. The δ(G*=0.1 MPa) is sensitive to both themolecular weight distribution and the long-chain branch but as far as acopolymer with Mw/Mn≦3 is concerned, the phase angle is indicative ofthe amount of the long-chain branch, and as the amount of the long-chainbranch is larger, the value of δ(G*=0.1 MPa) becomes smaller. If thevalue of δ(G*=0.1 MPa) is less than 40°, the amount of the long-chainbranch is too large and therefore, the mechanical strength decreases. Inthe copolymer of the present invention, Mw/Mn is 1.5 or more andtherefore, even when the copolymer has no long-chain branch, the valueof δ(G*=0.1 MPa) does not exceed 75°.

Furthermore, for attaining the objects of the present invention, thedifference T90−T10 (° C.) between the temperature T10 (° C.) allowing 10wt % of the total to elute in an integrated elution curve as determinedby the continuous temperature rising elution fractionation method (TREF)and the temperature T90 (° C.) allowing 90 wt % of the total to eluteand the weight average elution temperature Tw (° C.) preferably satisfythe following relationship:28−0.3×Tw≦T90−T10≦41−0.3×Tw

T90−T10 is a parameter indicating the width of the compositiondistribution and as this value is larger, the composition distributionis wider, that is, the difference in the α-olefin and/or polargroup-containing vinyl monomer contents is larger among differentmolecular chains. If the relationship of T90−T10≦41−0.3×Tw is notsatisfied, the composition distribution is wide and the low crystallinecomponent giving rise to stickiness and die lip build up is increased,as a result, the physical properties or outer appearance of the formedbody are impaired. On the other hand, it is difficult to produce acopolymer not satisfying 28−0.3×Tw≦T90−T10.

The parameter T90−T10 indicating the width of the compositiondistribution is expressed as a function of the average elutiontemperature Tw because of the following reasons. The average elutiontemperature Tw represents an average ethylene chain length of thecopolymer and as the Tw value is higher, the average chain length islonger. When the Tw value becomes low, that is, when the averageethylene chain length becomes short, this means that a larger amount ofshort-chain branches or the like which inhibit the crystallization areintroduced into the molecular chain. Usually, in a random copolymer,short-chain branches are not introduced at regular intervals but theinterval has a distribution and when many short-chain branches areintroduced, the interval distribution is broadened. As a result, even inthe case of a copolymer polymerized using the same catalyst, whenT90−T10 is plotted with respect to Tw, a right-rising relationship isobtained. The same applies to a copolymer produced using theconventional metallocene-based catalyst. The coefficient 0.3 of Tw is anexperimental value obtained from the gradient of the Tw vs. T90−T10 plotof an ethylene-hexene-1 copolymer polymerized using a metallocenecatalyst having uniform active sites. Also, the intercept 28 in theexpression of lower limit of the formula above is determined based onthe average elution temperature of an ethylene homopolymer, that is,about 95° C., such that T90−T10 becomes about 0 when Tw=95° C. On theother hand, the intercept 41 in the expression of upper limit isdetermined based on the fact that all Examples of the present inventionare covered.

MFR of the copolymer of the present invention is preferably from 0.01 to100, more preferably from 0.02 to 30, still more preferably from 0.05 to10. If MFR is less than 0.01, moldability is poor, whereas if it exceeds100, the strength decreases.

The mechanical properties of an ethylene-based copolymer by theconventional metallocene system containing no polar group aresubstantially determined by the average molecular weight and thecomonomer content, because both the composition distribution and themolecular weight distribution are narrow.

Meanwhile, (surprisingly), despite the same narrow compositiondistribution and narrow molecular weight distribution as those of anethylene-based copolymer by the conventional metallocene system,mechanical properties of the copolymer of the present invention are notan extension of the ethylene-based copolymer by the conventionalmetallocene system. More specifically, the elastic modulus and yieldingstress vary in correspondence to the monomer content and therefore, forexample, even a copolymer having the same elastic modulus or yieldingstress can be obtained as a copolymer excellent in the heat resistance.

The reason therefor is not clearly known but is presumed to be that boththe polar group moiety and the α-olefin-derived short-chain branchmoiety in the copolymer are kept away from the crystal portion of thepolyethylene and unevenly distributed in a high concentration to thenon-crystal portion and because of poor compatibility due to differencein the polarity, they cause an increase in the free volume of thenon-crystal part.

As additional conditions for attaining the objects of the presentinvention, the total amount of branches except for branch structuresderived from the side chain substituent represented by R¹⁷ in theformula above of the α-olefin and the COO(R¹⁹) group of the(meth)acrylic acid (or ester) is preferably 1/1,000 C or less.

Out of (meth)acrylic acid (or ester) monomer units forming the ternarycopolymer of ethylene-α olefin-(meth)acrylic acid (or ester) of thepresent invention, the amount of (meth)acrylic acid (or ester) monomerunits present in the terminal of the copolymer is preferably 20% orless, more preferably 5% or less, still more preferably 1% or less,based on the amount of all (meth)acrylic acid (or ester) monomer unitscontained in the copolymer, and it is preferred that a (meth)acrylicacid (or ester) monomer unit is substantially not present in theterminal. If the ratio of the unit present in the terminal exceeds 20%,the impact strength or elongation characteristic of the copolymerbecomes insufficient.

9. Method for Controlling Ternary Copolymer of Ethylene-αOlefin-(Meth)Acrylic Acid (or Ester)

The ternary copolymer of the present invention must have a molecularweight distribution where Mw/Mn is 1.5 or more and Mw/Mn is 3.0 or less,and Mw/Mn is preferably 2.7 or less, more preferably 2.4 or less.

As regards the control method therefor, the ternary copolymer above canbe produced by using the above-described α-olefin polymerizationcatalyst containing a component obtained by reacting the specifictriarylphosphine compound, particularly a component where either one ofR¹ and R² and either one of R³ and R⁴ are a secondary alkyl group, witha Group 10 transition metal compound, particularly a Pd compound. Thisconsidered to be achieved because the catalyst above is less susceptibleto deterioration of the active site even in the presence of a polarmonomer and maintains homogeneous active species. Furthermore, byreducing the change in the temperature or the monomer or comonomerconcentration during the polymerization, a copolymer with a narrowmolecular weight distribution can be produced. Here, Mw/Mn can be madesmall to a certain extent by such a technique, but it is difficult toproduce a copolymer having Mw/Mn of less than 1.5.

In the ternary copolymer of the present invention, the melting point Tm(° C.), the α-olefin content [C] (mol %) and the polar group-containingvinyl monomer content [X] (mol %) must satisfy the relationship of60≦Tm≦135−6.4×([C]+[X]). For this purpose, copolymerization must becaused to proceed so that a composition the α-olefin and the polargroup-containing vinyl monomer can be homogenized in the composition.

As regards the control method therefor, in the case of the comonomercontent, the pressure and concentration ratio of the ethylene, α-olefinand polar group-containing vinyl monomer are controlled, whereby themelting point Tm (° C.) and the contents of the α-olefin and the polargroup-containing vinyl monomer can be changed and the melting point canbe controlled. Although it depends on the ethylene pressure, forexample, when the ethylene pressure is 2 MPa, a copolymer having adesired comonomer content in the range of the α-olefin and the polargroup-containing vinyl monomer being from 0.01 to 9.0 mol/L can beproduced and the melting point can be controlled. Also, theabove-described α-olefin polymerization catalyst containing a componentobtained by reacting the specific triarylphosphine compound,particularly a component where either one of R¹ and R² and either one ofR³ and R⁴ are a secondary alkyl group, with a Group 10 transition metalcompound, particularly a Pd compound, is less susceptible todeterioration of the active site even in the presence of a polar monomerand maintains homogeneous active species. Furthermore, in addition tothe copolymerizability of the polar monomer, the copolymerizability of1-hexene which has been heretofore difficult to copolymerize is improvedas compared with the conventionally known catalyst, Accordingly, foreffecting the control above, it is important to select the catalyst ofthe present invention.

Also, in the ternary copolymer of the present invention, the phase angleδ(G*=0.1 MPa) at G*=0.1 MPa as measured by a rotary rheometer ispreferably 40° or more. The δ(G*=0.1 MPa) is indicative of the amount ofthe long-chain branch and when the amount of the long-chain branch islarge, the value of δ(G*=0.1 MPa) becomes small. If the value ofδ(G*=0.1 MPa) is less than 40°, the amount of the long-chain branch istoo large and therefore, the mechanical strength decreases.

For the control thereof, it is important to reduce the change in themonomer or comonomer concentration during polymerization or in thepolymerization temperature by using the above-described α-olefinpolymerization catalyst containing a component obtained by reacting thespecific triarylphosphine compound, particularly a component whereeither one of R¹ and R² and either one of R³ and R⁴ are a secondaryalkyl group, with a Group 10 transition metal compound, particularly aPd compound. Production of the long-chain branch also depends on thepolymerization solvent, and selection of the above-described hydrocarbonsolvent is important. The solubility of the copolymer for a solvent isconsidered to affect the production of the long-chain branch, and thecontrol can be effected also by selecting the comonomer content and thesolvent species. In the case of a solvent for which the polymer has highsolubility and in a copolymer having a high comonomer content, the phaseangle δ(G*=0.1 MPa) tends to become large, and the phase angle δ(G*=0.1MPa) can be made small, for example, by using hexane or the like forwhich the polymer has low solubility.

As a characteristic feature of the copolymer of the present invention,the difference T90−T10 (° C.) between the temperature T10 (° C.)allowing 10 wt % of the total to elute in an integrated elution curve asdetermined by the continuous temperature rising elution fractionationmethod (TREF) and the temperature T90 (° C.) allowing 90 wt % of thetotal to elute and the weight average elution temperature Tw (° C.)preferably satisfy the following relationship:28−0.3×Tw≦T90−T10 41−0.3×Tw

T90−T10 is a parameter indicating the width of the compositiondistribution and as regards the control method, the above-describedα-olefin polymerization catalyst containing a component obtained byreacting the specific triarylphosphine compound, particularly acomponent where either one of R¹ and R² and either one of R³ and R⁴ area secondary alkyl group, with a Group 10 transition metal compound,particularly a Pd compound, is less susceptible to deterioration of theactive site even in the presence of a polar monomer and maintainshomogeneous active species, so that a polymer having homogeneousmolecular chains can be produced. Furthermore, by reducing the change inthe temperature or the monomer or comonomer concentration during thepolymerization, a copolymer with a narrow molecular weight distributioncan be produced.

MFR of the copolymer of the present invention is preferably from 0.01 to100, more preferably from 0.02 to 30, still more preferably from 0.05 to10. If MFR is less than 0.01, moldability is poor, whereas if it exceeds100, the strength decreases.

As regards the control method therefor, MFR can be increased/decreasedby raising/lowering the polymerization temperature or can also becontrolled by the above-described normal molecular weight controllingmethod. Furthermore, in use of the above-described α-olefinpolymerization catalyst containing a component obtained by reacting thespecific triarylphosphine compound, particularly a component whereeither one of R¹ and R² and either one of R³ and R⁴ are a secondaryalkyl group, with a Group 10 transition metal compound, particularly aPd compound, MFR can be controlled by controlling the structures of R¹to R⁴.

As additional conditions for attaining the objects of the presentinvention, the total amount of branches except for branch structuresderived from the side chain substituent represented by R¹⁷ in theformula above of the α-olefin as the component (a) and the CO₂(R¹⁹)group of the (meth)acrylic acid (or ester) as the component (b) ispreferably 1/1,000C or less.

As regards the control method therefore, in the use of theabove-described α-olefin polymerization catalyst containing a componentobtained by reacting the specific triarylphosphine compound,particularly a component where either one of R¹ and R² and either one ofR³ and R⁴ are a secondary alkyl group, with a Group 10 transition metalcompound, particularly a Pd compound, the total amount of branches canbe controlled by controlling the selection of R¹ to R⁴. The total amountof branches can be also increased/decreased by raising/lowering thepolymerization temperature.

Out of (meth)acrylic acid (or ester) monomer units forming the ternarycopolymer of ethylene-α olefin-(meth)acrylic acid (or ester) of thepresent invention, the amount of (meth)acrylic acid (or ester) monomerunits present in the terminal of the copolymer is preferably 20% orless, more preferably 5% or less, still more preferably 1% or less,based on the amount of all (meth)acrylic acid (or ester) monomer unitscontained in the copolymer, and it is preferred that a (meth)acrylicacid (or ester) monomer unit is substantially not present in theterminal.

As regards the control method therefor, in the use of theabove-described α-olefin polymerization catalyst containing a componentobtained by reacting the specific triarylphosphine compound,particularly a component where either one of R¹ and R² and either one ofR³ and R⁴ are a secondary alkyl group, with a Group 10 transition metalcompound, particularly a Pd compound, the control can be effected byselecting the structures of R¹ to R⁴.

The copolymer of the present invention preferably contains noheterogeneous bond based on 1,2-insertion.

As regards the control method therefor, in the use of theabove-described α-olefin polymerization catalyst containing a componentobtained by reacting the specific triarylphosphine compound,particularly a component where either one of R¹ and R² and either one ofR³ and R⁴ are a secondary alkyl group, with a Group 10 transition metalcompound, particularly a Pd compound, the control can be effected byselecting the structures of R¹ to R⁴.

EXAMPLES

The present invention is described in greater detail by referring toExamples and Comparative Examples, and the configurations of the presentinvention are verified to have reasonableness, significance andsuperiority to conventional techniques by the data in preferred Examplesand the comparison of Examples with Comparative Examples. The structuresof ligands used in Examples and Comparative Examples are shown in Table1.

TABLE 1

(I)

(II)

(III)

(IV)

(V)

(VI)

(VII)

(VIII)

(IX)

(X)

(XI)

(XII)

(XIII)

(XIV)

Also, in Examples, the following abbreviations were used.

-   Pd(dba)2: Bis(dibenzilideneacetone)palladium-   Ni(cod)2: Bis(cyclooctadiene)nickel-   MA: Methyl acrylate-   EA: Ethyl acrylate-   tBA: Tertiary-butyl acrylate-   MMA: Methyl methacrylate-   AA: Acrylic acid-   VA: Vinyl acetate-   LUA: Lauryl acrylate-   HEA: 2-Hydroxyethyl acrylate-   EUA: Ethyl undecylenate-   NBMOH: (5-Norbornene)-2-methanol-   NBYA: (5-Norbornen)-2-yl acetate-   ATMS: Allyltriethoxysilane-   BTOH: (3-Buten)-1-ol-   TPB: Triphenylborane-   clay: Sulfuric acid/lithium sulfate-treated montmorillonite    1. Evaluation Method    (1) Molecular Weight and Molecular Weight Distribution (Mw, Mn, Q    Value)    (Measurement Conditions)

Model of apparatus used: 150 C manufactured by Waters Corp., detector:MIRAN 1A•IR Detector manufactured by FOXBORO (measurement wavelength:3.42 μm), measurement temperature: 140° C., solvent:orthodichlorobenzene (ODCB), column: AD806M/S (three columns)manufactured by Showa Denko K.K., flow rate: 1.0 mL/min, amountinjected: 0.2 mL.

(Preparation of Sample)

As the sample, a 1 mg/mL solution was prepared using ODCB (containing0.5 mg/mL of BHT (2,6-di-tert-butyl-4-methylphenol)) and dissolving itat 140° C. over about 1 hour.

(Calculation of Molecular Weight)

The calculation was performed by the standard polystyrene method, andthe conversion from retention volume to molecular weight was performedusing a previously prepared calibration curve with standardpolystyrenes.

The standard polystyrenes used all are brand names of Tosoh Corporation,that is, F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500 andA1000. A solution was prepared by dissolving each standard polystyrenein ODCB (containing 0.5 mg/mL of BHT) to have a concentration of 0.5mg/mL, and 0.2 mL of the solution was injected to prepare a calibrationcurve. The calibration curve employs a cubic expression obtained byapproximation using the least squares method. For the viscosity equation([η]=K×M^(α)) used in the conversion to molecular weight, the followingnumerical values were used.

PS: K=1.38×10⁻⁴, α=0.7

PE: K=3.92×10⁻⁴, α=0.733

PP: K=1.03×10⁻⁴, α=0.78

(2) Melting Point (Tm)

Using a differential scanning calorimeter, DSC6200 manufactured by SeikoInstrument Co., Ltd., 5 mg of the sample strip in a sheet form waspacked in the aluminum pan, and the temperature was once raised fromroom temperature to 200° C. at a temperature rise rate of 100° C./min,held for 5 minutes, then dropped to 20° C. at 10° C./min to effectcrystallization, and again raised to 200° C. at 10° C./min, whereby amelting curve was obtained.

The peak top temperature of the main endothermic peak in the finaltemperature rise stage performed to obtain the melting curve was definedas the melting point Tm and the peak area of the peak was indicated byΔHm.

(3) Comonomer (α-Olefin, (Meth)Acrylic Acid (or Ester)) Content

The comonomer content, that is, the content of α-olefin monomer unit asthe component (a) and the content of the (meth)acrylic acid (or ester)monomer unit as the component (b), in the copolymer was measured by thefollowing two methods.

(3-1) Measurement of Comonomer Content by ¹³C-NMR

[Preparation of Sample]

About 250 mg of the sample formed into a film shape of about 100 μm inthickness was weighed in a test tube having an outer diameter of 10 mm,and 1.84 ml of ortho-dichlorobenzene and 0.46 ml of deuteratedbromobenzene were added. After the upper part of the test tube waspurged with nitrogen, the test tube was closed by a lid, and the mixturewas heated and dissolved in a high-temperature tank at 130° C. until thesample became uniform.

[¹³C-NMR Measurement]

The measurement was performed using a cryoprobe-equipped NMR measurementdevice, AVANCE III400, manufactured by Bruker-Biospin under theconditions of gated proton decoupling and no NOE decoupling. The flipangle of the excitation pulse was set to 90°, the pulse interval was setto 16.3 seconds, the measurement temperature was set to 120° C., thecumulated number was set to 500 times or more, and the observed spectrumwidth was set to 24,038.5 Hz.

Assignments of the ¹³C-NMR spectrum were performed by referring tovarious publications. In the case where the α-olefin is propylene and ishexene and in the case where the polar group-containing vinyl monomer ismethyl acrylate and is ethyl acrylate, the partial structures, marks andchemical shifts of the ¹³C-NMR resonant peak are shown in ChemicalFormulae 9 to 12 below.

[Determination of α-Olefin Content and Polar Group-Containing VinylMonomer Content]

The amount T_(E) proportional to the molar number of the ethylene unit,the amount T_(α-0) proportional to the molar number of the α-olefinunit, and the molar number T_(F) of the polar group-containing vinylmonomer unit were determined from the obtained ¹³C-NMR spectrum, and theα-olefin content (unit: mol %) and the polar group-containing vinylmonomer content (unit: mol %) were determined according toT_(α-0)/(T_(E)+T_(α-0)+T_(F))×100 and T_(F)/(T_(E)+T_(α-0)+T_(F))×100,respectively.

In the case where the component (a) is propylene and is 1-hexene and inthe case where the component (b) is methyl acrylate and is ethylacrylate, T_(α-0) and T_(F) were determined as follows.

[In the Case where the Component (a) is Propylene]

Out of nuclear magnetic resonant peaks produced when propylene wasinserted into the chain upon copolymerization, the average value of ½ ofthe integrated intensity of peaks derived from α methylene carbon in thevicinity of 37.6 ppm and the integrated intensity of peaks derived frommethine carbon in the vicinity of 33.2 ppm was determined as the amountT_(α-0) proportional to the molar number of the propylene unit.T_(α-0)=(I_(37.6)/2+I_(33.2))/2. Here, for example, I_(37.6) is theintegrated intensity of peaks derived from α methylene carbon appearingin the vicinity of 37.6 ppm.

[In the Case where the Component (a) is 1-Hexene]

Similarly to propylene, the amount T_(α-0) proportional to the molarnumber of the hexene unit was determined using characteristic peaksproduced by 1-hexene according to the following formula.T_(α-0)=(I_(27.3)/2+I_(34.2)+I_(34.6)/2)/3. Here, I_(27.3) is theintegrated intensity of peaks due to resonance of β methylene appearingin the vicinity of 27.3 ppm by the copolymerization of 1-hexene,I_(34.2) is the integrated intensity of resonant peaks attributable tothe fourth carbon counting from the branch end of the butyl branchproduced by the copolymerization of 1-hexene, and I_(34.6) is theintegrated intensity of peaks due to resonance of α methylene.

[In the Case where the Component (b) is Methyl Acrylate]

Out of nuclear magnetic resonance signals produced due tocopolymerization of methyl acrylate, the average value of half of theintegrated intensity of 3 methylene carbon in the vicinity of 27.8 ppm,half of the integrated intensity of a methylene carbon in the vicinityof 32.8 ppm, and the integrated intensity of methine carbon in thevicinity of 46.0 ppm was determined as the amount (T_(F)) proportionalto the molar number of the methyl acrylate unit.T_(F)=(I_(27.8)/2+I_(32.8)/2+I_(46.0))/3.

[In the Case where the Component (b) is Ethyl Acrylate]

Similarly to methyl acrylate, out of nuclear magnetic resonance signalsproduced due to copolymerization of ethyl acrylate, the average value ofhalf of the integrated intensity of β methylene carbon in the vicinityof 27.8 ppm, half of the integrated intensity of α methylene carbon inthe vicinity of 32.8 ppm, and the integrated intensity of methine carbonin the vicinity of 46.0 ppm was determined as the amount (T_(F))proportional to the molar number of the ethyl acrylate unit.T_(F)=(I_(27.8)/2+I_(32.8)/2+I_(46.0))/3. Incidentally, the amount T_(E)proportional to the molar number of the ethylene unit was determined asa value obtained by adding half of the integrated intensity of all αmethylene carbon peaks produced by the above-described respectivecomonomers and the integrated intensity of all β methylene carbon peaksto the integrated intensity of main peaks including γ methylene in thevicinity of 30 ppm, and multiplying the resulting value by ½.T_(E)=(I₃₀+I_(α)/2+I_(β))/2. Here, I₃₀ is the integrated intensity ofmain peaks including γ methylene in the vicinity of 30 ppm, and I_(α) isI_(37.6)+I_(32.8) when the comonomers are propylene and methyl acrylate,and I_(34.6)+I_(32.8) when the comonomers are 1-hexene and ethylacrylate.

[Total Amount of Branches Except for Branch Structures Derived from theCopolymerized α-Olefin and Polar Group-Containing Vinyl Monomer]

A ¹³C-NMR spectral analysis was performed by referring toMacromolecules, 32(5), 1620 (1999) and while attribution of branchstructures except for branch structures derived from the copolymerizedα-olefin and polar group-containing vinyl monomer was performed, theamount of those branches per 1.000 carbon and the sum total thereof weredetermined by a known method.

Structure of Propylene Unit-Inserted Moiety and Marks

The value in the parenthesis is the chemical shift value of thecharacteristic peak of 13C-NMR.

Structure of 1-Hexene Unit-Inserted Moiety and Marks

The value in the parenthesis is the chemical shift value of thecharacteristic peak of 13C-NMR.

Structure of Ethyl Acrylate Unit-Inserted Moiety and Marks

The value in the parenthesis is the chemical shift value of thecharacteristic peak of 13C-NMR.

Structure of Ethyl Acrylate Unit-Inserted Moiety and Marks

The value in the parenthesis is the chemical shift value of thecharacteristic peak of 13C-NMR.

(3-2) Measurement of (Meth)Acrylic Acid (or Ester) Monomer Content by IR

As the analysis sample, a press plate of about 0.5 mm was produced, andits infrared absorption spectrum was obtained using Model FTIR-8300manufactured by Shimadzu Corporation. The comonomer content wascalculated based on the overtone absorption of carbonyl group in thevicinity of 3,450 cm⁻¹ and the infrared absorption intensity ratio ofolefin absorption in the vicinity of 4,250 cm⁻¹. For the calculation, acalibration curve prepared by the ¹³C-NMR measurement above was used.

In the present invention, the above-described two kinds of method areemployed. The analysis by IR is a simple method but the analysisaccuracy is relatively low compared with the analysis by ¹³C-NMR. InExamples of the present invention, when values of both analyses arepresent, the analysis value by ¹³C-NMR is employed.

(4) Composition Distribution Measurement by TREF

The measurement was performed using an apparatus manufactured by JapanPolyethylene Corp. by the following procedure under the followingconditions.

(4-1) Sample

The sample (20 mg) and 20 mL of o-dichlorobenzene were weighed in 20mL-volume vial, and the vial was closed by a metal-made screw cap andthen placed in a dry bath kept at 140° C. The mixture was dissolved for2 hours while stirring by hand every 15 minutes and after the completionof dissolution, the absence of insoluble components was confirmed withan eye.

(4-2) Deposition

Deposition was performed using an apparatus where a 400 W heater and athermocouple are attached to an aluminum block processed to gaplesslyhouse a stainless steel column having an inner diameter of 8 mm and alength of 120 mm (manufactured by Japan Polyethylene Corp.). The columnwas previously packed with glass beads and kept at 140° C. in theapparatus above. The sample solution at 140° C. was injected thereintoand subsequently, the aluminum block housing the column was cooled toroom temperature at a rate of 4° C./h, whereby the sample was depositedon the glass bead.

(4-3) Elution

The elution was performed using an apparatus where a Peltier device, a200 W heater and a thermocouple are attached to an aluminum blockprocessed to gaplessly house a stainless steel column having an innerdiameter of 8 mm and a length of 120 mm and a stainless steel tubehaving an outer diameter of 1/16 inches and being connected to thecolumn (manufactured by Japan Polyethylene Corp.). An infraredspectrometer, MIRAN Model 1A, equipped with a pump for LC, Model L-6200,manufactured by Hitachi Ltd, a thermally insulated lead pipe and aliquid flow cell was connected to the apparatus to fabricate a systemwhere the amount of the sample in a solvent can be measured by flowingthe solvent at a constant flow rate while heating the column at aconstant rate. The column after the completion of deposition was housedin the system, the measurement wavelength of the infrared spectrometerwas set to 3.42 μm, o-dichlorobenzene was flowed at a flow rate of 1.0mL/min for about 30 minutes at 20° C., and the base line was stabilized.Subsequently, while flowing o-dichlorobenzene at a flow rate of 1.0mL/min, the temperature was raised to 130° C. at a rate of 50° C./h, andthe temperature during this period and the output of the infraredspectrometer were recorded by a computer. The obtained chromatogram wasprocessed to obtain an elution temperature-elution amount curve.Incidentally, when the elution starting temperature apparently fellbelow 20° C., the temperature was dropped to 0° C. at a rate of 4° C./hwithout flowing o-dichlorobenzene before the elution operation, theno-dichlorobenzene was flowed at a flow rate of 1.0 mL/min for about 30minutes at 0° C. and after the base line was stabilized, while flowingo-dichlorobenzene at a flow rate of 1.0 mL/min, the temperature wasraised to 130° C. at a rate of 50° C./h, whereby the measurement wasperformed. From the data obtained, the weight average elutiontemperature Tw was calculated according to the following formula.

$\begin{matrix}{{Tw} = \frac{\sum\;{{I(T)} \times T}}{\sum\; I}} & \left\lbrack {{Math}.\mspace{14mu} 1} \right\rbrack\end{matrix}$

Here, T represents the elution temperature and I(T) represents theelution amount at a temperature T (° C.). Also, T90 and T10 are theelution temperatures at elution amounts of 90 wt % and 10 wt %,respectively, based on the total.

(5) Measurement of δ(G*=0.1 MPa) by Dynamic Viscoelasticity Measurement

The resin tested was press-molded at 160° C. into a circular form of 25mm in diameter and 1 mm in thickness, and this was used as the sample.As the apparatus for measuring the dynamic viscoelastic characteristics,a rotary rheometer, Model ARES, manufactured by Rheometrics and aparallel plate of 25 mm in diameter were used. The dynamicviscoelasticity was measured in a nitrogen atmosphere under thefollowing conditions.

-   -   Temperature: 160° C.    -   Distortion amount: 10%    -   Measurement angular frequency range: 1.0×10⁻² to 1.0×10² rad/s    -   Measurement interval: 5 points/decade

The phase angle δ was plotted with respect to the common logarithm logG* of the complex modulus G*(Pa), and the value of δ(°) at a pointcorresponding to log G*=5.0 was determined as δ(G*=0.1 MPa). In the casewhere the measurement points lacked the point corresponding to logG*=5.0, the δ value at log G*=5.0 was determined by linear interpolationusing two points before and after log G*=5.0. Also, when log G*<5 in allof the measurement points, the 8 value at log G*=5.0 was determined byextrapolation of the quadratic curve using the values at three pointsfrom the larger log G* value side.

(6) Measurement of Tensile Modulus, Tensile Yield Stress, NominalTensile Stress at Break and Nominal Tensile Strain at Break by TensileTest

A small test piece of form 5B described in JIS K7162 obtained bypreparing a sheet of 1 mm in thickness by the method described in JISK7151 (Cooling Method A) from the ethylene-based copolymer of eachExample and punching the sheet was subjected to a tensile test under theconditions of a tensile speed of 10 mm/min and a temperature of 23° C.,and from the obtained stress-strain curve, the tensile modulus, tensileyield stress, nominal tensile stress at break and nominal tensile strainat break were calculated by the method described in Seikei Kakou(Molding Process), Vol. 4, No. 8, pp. 489-496 (1992). Incidentally, thetensile yield stress was assigned to the true stress at the maximumpoint when a distinct maximum point is present in the nominalstress-strain curve, and assigned to the true stress at the inflectionpoint in the true stress-true strain curve when such a maximum point islacking. For the calculation of strain, a displacement between chuckswas used.

(7) Tensile Impact Strength

A test piece of form 4 described in JIS K7160 was produced by preparinga sheet of 1 mm in thickness by the method described in JIS K7151(Cooling Method A) from the ethylene-based copolymer of each Example andpunching the sheet, and the measurement was performed by using this testpiece under the conditions described in JIS K7160.

(8) Wettability Test

A sheet of 1 mm in thickness was prepared by the method described in JISK7151 (Cooling Method A), and the sheet was dipped in ethanol containedin a beaker and then subjected to ultrasonic washing for 1 minute. Afterlightly wiping off the ethanol with gauze, an about 1 cm-squarecharacter was written on the surface thereof by using an aqueous feltpen “RIB” MyT-7 produced by Mitsubishi Pencil Co., Ltd., and thewettability was judged by the shape of the character after 10 seconds.The criteria of A, B, C and D are as follows.

A: Liquid was not or scarcely repelled and the outline of the characteris clear.

B: Liquid was slightly repelled, but the line of the character wasscarcely broken.

C: Liquid was repelled, and the line of the character was broken inspots.

D: Liquid was strongly repelled, and the line of the character wasbroken everywhere.

2. Synthesis of Ligand

Ligands obtained in Synthesis Examples below were used. In the followingSynthesis Examples, unless otherwise indicated, the operation wasperformed in a purified nitrogen atmosphere, and the solvent was usedafter its dehydration and deoxidation.

(Synthesis Example 1) Synthesis of Ligand (I)

A n-butyllithium hexane solution (2.5 M, 2 mL, 5 mmol) was slowly addeddropwise to a tetrahydrofuran (20 mL) solution of anhydrousbenzenesulfonic acid (400 mg, 2.5 mmol) at 0° C. The solution wasstirred for 1 hour while raising the temperature to room temperature.The reaction solution was cooled to −70° C. and after adding phosphorustrichloride (340 mg, 2.5 mmol), this mixture was stirred for 2 hourswhile raising the temperature to room temperature (Reaction Solution A).

A n-butyllithium hexane solution (2.5 M, 2 mL, 5 mmol) was slowly addeddropwise to a diethyl ether (20 mL) solution of1-bromo-2-isopropylbenzene (1 g, 5 mmol) at −30° C. The mixed solutionwas stirred for 3 hours while raising the temperature to roomtemperature. The solution was added dropwise to Reaction Solution A atroom temperature, and the mixed solution was stirred for one night.After the reaction, water (20 mL) was added, and the resulting solutionwas extracted with ether (20 mL×2) and washed with 1 N hydrochloric acid(20 mL×2). Thereafter, the solvent was removed by evaporation, and theresidue was washed with methanol (5 mL) to obtain 100 mg of the targetproduct as a white product.

1H NMR (CDCl3, ppm/d): 8.35 (ddd, J=0.8, 4.8, 7.6 Hz, 1H), 7.74 (tt.J=1.4, 7.6 Hz, 1H), 7.65 (t, J=7.6 Hz, 2H), 7.53 (t, J=6.4 Hz, 2H), 7.42(ddt, J=1.2, 2.8, 7.6 Hz, 1H), 7.26 (ddt, J=0.8, 4.8, 8.0 Hz, 2H), 7.05(dd, J=0.8, 7.6 Hz, 1H), 6.98 (dd, J=0.8, 5.2 Hz, 2H), 3.00 (m, 2H),1.15 (d, J=6.8 Hz, 6H), 1.09 (d, J=6.0 Hz, 6H). 31P NMR (CDCl3, ppm/d):9.5.

(Synthesis Example 2) Synthesis of Ligand (II)

A n-butyllithium hexane solution (2.5 M, 1.9 mL, 4.8 mmol) was slowlyadded dropwise to a tetrahydrofuran (10 mL) solution of anhydrousbenzenesulfonic acid (400 mg, 2.5 mmol) at 0° C. The mixed solution wasstirred for 1 hour while raising the temperature to room temperature.The reaction solution was cooled to −78° C. and after adding phosphorustrichloride (0.2 mL, 2.4 mmol), this mixture was stirred for 2 hours(Reaction Solution B).

A n-butyllithium hexane solution (2.5 M, 1.9 mL, 4.8 mmol) was addeddropwise to a tetrahydrofuran (10 mL) solution of1-bromo-2-(1′-methoxymethyl)ethylbenzene (1 g, 4.8 mmol) at 0° C. Themixed solution was stirred for 1 hour while raising the temperature toroom temperature. The obtained solution was added dropwise to ReactionSolution B at 0° C., and the mixed solution was stirred at roomtemperature for 3 hours. After removing the solvent by evaporation,water (100 mL) was added, and the resulting solution was made acidic(PH<3) by adding hydrochloric acid, then extracted with methylenechloride (100 mL×3) and dried over sodium sulfate. Thereafter, thesolvent was removed by evaporation, and the residue was recrystallizedfrom ethyl acetate/diethyl ether ( 1/10) to obtain the target product asa white product.

1H NMR (CDCl3, ppm/d): 8.30 (br, 1H), 7.60 (br, 3H), 7.50 (br, 2H), 7.40(br, 1H), 7.27 (br, 2H), 7.04 (br, 3H), 3.0 (br, 12H), 1.1 (br, 6H). 31PNMR (CDCl3, ppm/d): −8.5.

(Synthesis Example 3) Synthesis of Ligand (III)

A n-butyllithium hexane solution (2.5 M, 17.4 mL, 43.6 mmol) was slowlyadded dropwise to a tetrahydrofuran (200 mL) solution of anhydrousbenzenesulfonic acid (3.4 g, 21.8 mmol) at 0° C. The mixed solution wasstirred for 1 hour while raising the temperature to room temperature.The reaction solution was cooled to −78° C. and after adding phosphorustrichloride (1.9 mL, 21.8 mmol), this mixture was stirred for 2 hours(Reaction Solution C).

A tert-butyllithium hexane solution (1.6 M, 54.5 mL, 87.2 mmol) wasslowly added dropwise at −78° C. to a tetrahydrofuran (200 mL) solutionof 1-bromo-2-isopropyl-4-methoxybenzene (10 g, 43.6 mmol), and the mixedsolution was stirred for 1 hour. The obtained solution was addeddropwise to Reaction Solution C at −78° C., and the mixed solution wasstirred at room temperature for one night. After removing the solvent byevaporation, water (200 mL) was added, and the resulting solution wasmade acidic (PH<3) by adding hydrochloric acid, then extracted withmethylene chloride (100 mL×3) and dried over sodium sulfate. Thereafter,the solvent was removed by evaporation, and the residue wasrecrystallized from methanol to obtain 0.3 g of the target product as awhite product.

1H NMR (CDCl3, ppm/d): 8.34 (dd, J=5.2, 7.6 Hz, 1H), 7.71 (t, J=7.6 Hz,1H), 7.40 (m, 1H), 7.1-7.0 (m, 3H), 6.91 (dd, J=8.8, 14.4 Hz, 2H), 6.75(d, J=8.4 Hz, 2H), 3.80 (s, 6H), 2.97 (m, 2H), 1.15 (d, J=6.8 Hz, 6H),1.08 (br, 6H). 31P NMR (CDCl3, ppm/d: −10.7.

(Synthesis Example 4) Synthesis of Ligand (IV)

A n-butyllithium hexane solution (2.5 M, 10 mL, 25.3 mmol) was slowlyadded dropwise to a tetrahydrofuran (50 mL) solution of anhydrousbenzenesulfonic acid (2 g, 12.6 mmol) at 0° C. The mixed solution wasstirred for 1 hour while raising the temperature to room temperature.The reaction solution was cooled to −78° C. and after adding phosphorustrichloride (1.0 mL, 12.6 mmol), this mixture was stirred for 2 hours(Reaction Solution D).

A tert-butyllithium hexane solution (1.6 M, 31.6 mL, 50.6 mmol) wasslowly added dropwise at 0° C. to a tetrahydrofuran (50 mL) solution of1-bromo-2-cyclohexylbenzene (6 g, 25.3 mmol), and the mixed solution wasstirred for 1 hour. The obtained solution was added dropwise to ReactionSolution D at −78° C., and the mixed solution was stirred at roomtemperature for one night. LC-MS Purity: 50%. After adding water (200mL), the resulting solution was made acidic (PH<3) by addinghydrochloric acid, then extracted with methylene chloride (100 mL×3) anddried over sodium sulfate. Thereafter, the solvent was removed byevaporation, and the residue was purified by silica gel columnchromatography (dichloromethane/methanol=50/1) to obtain 1.0 g of thetarget product as a white product.

1H NMR (CDCl3, ppm/d): 7.86 (m, 1H), 7.30 (dt, J=1.2, 7.6 Hz, 1H),7.24-7.15 (m, 5H), 6.96 (m, 2H), 6.83 (m, 1H), 6.57 (m, 2H), 3.21 (br,2H), 1.55 (br, 8H), 1.31 (br, 4H), 1.14 (br, 8H). 31P NMR (CDCl3,ppm/d): −28.7.

(Synthesis Example 5) Synthesis of Ligand (V)

A n-butyllithium hexane solution (2.5 M, 4.6 mL, 11.5 mmol) was slowlyadded dropwise to a tetrahydrofuran (20 mL) solution of anhydrousbenzenesulfonic acid (0.9 g, 5.8 mmol) at 0° C. The mixed solution wasstirred for 1 hour while raising the temperature to room temperature.The reaction solution was cooled to −78° C. and after adding phosphorustrichloride (0.5 mL, 5.8 mmol), this mixture was stirred for 2 hours at0° C. (Reaction Solution E).

A tert-butyllithium hexane solution (1.5 M, 15.4 mL, 23 mmol) was addeddropwise at 0° C. to a tetrahydrofuran (50 mL) solution of1-bromo-2-hydrofurylbenzene (2.6 g, 11.5 mmol), and the mixed solutionwas stirred for 1 hour. The obtained solution was added dropwise toReaction Solution E at −50° C., and the mixed solution was stirred atroom temperature for one night. After removing the solvent byevaporation, water (100 mL) was added, and the resulting solution waswashed with MTBE (100 mL×3), made acidic (PH<3) by adding hydrochloricacid, then extracted with methylene chloride (100 mL×3) and dried oversodium sulfate. Thereafter, the solvent was removed by evaporation, andthe residue was washed with methanol to obtain 1.0 g of the targetproduct as a white product.

1H NMR (DMSO, ppm/d): 7.88 (m, 3H), 7.42 (m, 2H), 7.37-7.29 (m, 3H),7.22 (t, J=7.4 Hz, 1H), 7.11 (t, J=7.4 Hz, 2H), 6.72 (m, 1H), 6.63 (m,2H), 5.27 (br, 2H), 3.94 (m, 2H), 3.67 (m, 2H), 2.0-1.1 (br, 8H). 31PNMR (CDCl3, ppm/d): −30.4.

(Synthesis Example 6) Synthesis of Ligand (VI)

A n-butyllithium hexane solution (2.5 M, 11.6 mL, 29 mmol) was slowlyadded dropwise to a tetrahydrofuran (100 mL) solution of anhydrousbenzenesulfonic acid (2.3 g, 14.5 mmol) at 0° C. The mixed solution wasstirred for 1 hour while raising the temperature to room temperature.The reaction solution was cooled to −78° C. and after adding phosphorustrichloride (1.26 mL, 14.5 mmol), this mixture was stirred for 2 hours(Reaction Solution F).

A n-butyllithium hexane solution (1.6 M, 11.6 mL, 29 mmol) was addeddropwise at 0° C. to a diethyl ether (100 mL) solution of1-bromo-2-tert-butylbenzene (6.2 g, 29 mmol), and the mixed solution wasstirred for 1 hour. The obtained solution was added dropwise to ReactionSolution F at −78° C., and the mixed solution was stirred at roomtemperature for one night. After removing the solvent by evaporation,water (100 mL) was added, and the resulting solution was made acidic(PH<3) by adding hydrochloric acid, then extracted with methylenechloride (100 mL×3) and dried over sodium sulfate. Thereafter, thesolvent was removed by evaporation, and the residue was recrystallizedfrom methanol to obtain 3.5 g of the target product as a white product.

1H NMR (CDCl3, ppm/d): 8.33 (dd, J=5.2, 7.6 Hz, 1H), 7.7 (m, 3H), 7.62(t, J=7.6 Hz, 1H), 7.55 (t, J=7.6 Hz, 1H), 7.38 (m, 1H), 7.25 (t, J=7.6Hz, 1H), 7.2-7.1 (m, 3H), 6.90 (dd, J=8.0, 14.0 Hz, 1H), 1.37 (s, 9H),1.34 (s, 9H). 31P NMR (CDCl3, ppm/d): 4.5.

(Synthesis Example 7) Synthesis of Ligand (VII)

A n-butyllithium hexane solution (2.5 M, 4.7 mL, 11.8 mmol) was slowlyadded dropwise to a diethyl ether (10 mL) solution of1-bromo-2-isopropylbenzene (2.34 g, 11.8 mmol) at −30° C. The mixedsolution was stirred for 2 hours while raising the temperature to roomtemperature. The reaction solution was added to a tetrahydrofuransolution of phosphorus trichloride (0.81 g, 5.88 mmol) at −78° C., andthe mixed solution was stirred for 2 hours at the same temperature(Reaction Solution G).

A tert-butyllithium hexane solution (1.6 M, 5.9 mL, 9.4 mmol) was slowlyadded dropwise at −78° C. to a tetrahydrofuran (12 mL) solution of1-bromo-2-sulfonic acid isopropyl ester-4-methoxybenzene (1.5 g, 4.7mmol), and the mixed solution was stirred for 4 hours. The obtainedsolution was added dropwise to Reaction Solution G at −78° C., and themixed solution was stirred at room temperature for one night. Afteradding water (20 mL), the resulting solution was made acidic (PH<2) byadding hydrochloric acid, then extracted with methylene chloride (50mL×3), washed with an aqueous sodium chloride solution and dried oversodium sulfate. Thereafter, the solvent was removed by evaporation(yield: 1.2 g). This product was dissolved in methanol (8 mL), and anaqueous sodium hydroxide solution (1 M, 4 mL, 4 mmol) andtetrahydrofuran (8 mL) was added thereto. The resulting mixture wasstirred at 50° C. for 4 hours and after adding 2 N hydrochloric acid (20mL), the solution was extracted with methylene chloride (50 mL×3) anddried over sodium sulfate. Subsequently, the solvent was removed byevaporation, and the residue was washed with a small amount of diethylether to get the target product as a white product (yield: 0.3 g).

1H NMR (CDCl3, ppm/d): 7.94 (br, 1H), 7.68 (m, 2H), 7.59 (m, 2H), 7.31(m, 2H), 7.04 (m, 2H), 6.94 (d, J=2.8 Hz, 2H), 3.95 (s, 3H), 3.06 (m,2H), 1.19 (m, 12H). 31P NMR (CDCl3, ppm/d): −10.4.

(Synthesis Example 8) Synthesis of Ligand (VIII)

A n-butyllithium hexane solution (2.5 M, 5 mL, 12.6 mmol) was slowlyadded dropwise to a tetrahydrofuran (20 mL) solution of anhydrousbenzenesulfonic acid (1 g, 6.3 mmol) at 0° C. The mixed solution wasstirred for 1 hour while raising the temperature to room temperature.The reaction solution was cooled to −78° C. and after adding phosphorustrichloride (0.54 mL, 6.3 mmol), this mixture was stirred for 2 hours(Reaction Solution H).

A n-butyl lithium hexane solution (2.5 M, 5.0 mL, 12.6 mmol) was slowlyadded dropwise at 0° C. to a diethyl ether (20 mL) solution of1-bromo-2-(1′-methyl-2′-phenoxy)ethylbenzene (3.8 g, 12.6 mmol), and themixed solution was stirred for 2 hours at room temperature. The obtainedsolution was added dropwise to Reaction Solution H at room temperature,and the mixed solution was stirred at room temperature for one night.LC-MS Purity: 22%. After adding water, the resulting solution was madeacidic (PH<3) by adding hydrochloric acid, then extracted with methylenechloride (100 mL×3) and dried over sodium sulfate. Thereafter, thesolvent was removed by evaporation, and the residue was purified bysilica gel column chromatography (dichloromethane/methanol=70/1) toobtain 2.0 g of the target product as a white product.

1H NMR (DMSO, ppm/d): 8.34 (t, J=6.0 Hz, 1H), 7.70 (t, J=7.6 Hz, 1H),7.40 (m, 1H), 7.4-7.0 (m, 10H), 6.9-6.5 (m, 9H), 4.0 (m, 2H), 3.7 (m,4H), 1.1 (m, 3H), 0.8 (m, 3H). 31P NMR (CDCl3, ppm/d): −29.9.

(Synthesis Example 9) Synthesis of Ligand (IX)

A n-butyllithium hexane solution (2.5 M, 3 mL, 7.6 mmol) was slowlyadded dropwise to a tetrahydrofuran (10 mL) solution of anhydrousbenzenesulfonic acid (0.6 g, 3.8 mmol) at 0° C. The mixed solution wasstirred for 1 hour while raising the temperature to room temperature.The reaction solution was cooled to −78° C. and after adding phosphorustrichloride (0.33 mL, 3.8 mmol), this mixture was stirred for 2 hours(Reaction Solution I).

A n-butyl lithium hexane solution (2.5 M, 3.0 mL, 7.6 mmol) was slowlyadded dropwise at 0° C. to a diethyl ether (20 mL) solution of1-bromo-2-isopropyl-3-hexylbenzene (2.2 g, 7.6 mmol), and the mixedsolution was stirred for 3 hours at room temperature. The obtainedsolution was added dropwise to Reaction Solution I at −78° C., and themixed solution was stirred at room temperature for one night. LC-MSPurity: 51%. After adding water, the resulting solution was made acidic(PH<3) by adding hydrochloric acid, then extracted with methylenechloride (50 mL×3) and dried over sodium sulfate. Thereafter, thesolvent was removed by evaporation, and the residue was purified bysilica gel column chromatography (dichloromethane/methanol=70/1) toobtain 0.8 g of the target product as a white product.

1H NMR (CDCl3, ppm/d): 8.34 (d, J=6.0 Hz, 1H), 7.70 (d, J=7.6 Hz, 1H),7.40 (m, 1H), 7.29 (d, J=4.4 Hz, 2H), 7.04 (m, 3H), 6.85 (dd, J=7.6,14.8 Hz, 2H), 2.97 (m, 2H), 2.60 (t, J=7.6 Hz, 4H), 1.54 (m, 4H), 1.25(s, 12H), 1.2-1.0 (m, 12H), 0.82 (br, 6H). 31P NMR (CDCl3, ppm/d): −9.9.

(Synthesis Example 10) Synthesis of Ligand (X)

A n-butyllithium hexane solution (2.5 M, 10 mL, 25.3 mmol) was slowlyadded dropwise to a tetrahydrofuran (20 mL) solution of anhydrousbenzenesulfonic acid (2 g, 12.6 mmol) at 0° C. The mixed solution wasstirred for 1 hour while raising the temperature to room temperature.The reaction solution was cooled to −78° C. and after adding phosphorustrichloride (1.0 mL, 12.6 mmol), this mixture was stirred for 2 hours(Reaction Solution J1).

Mg was dispersed in tetrahydrofuran (20 mL) and after adding1-bromo-2-methoxybenzene (2.3 g, 12.6 mmol), the mixture was stirred for3 hours at room temperature. The resulting solution was added dropwiseto Reaction Solution J1 at −78° C., and the mixture was stirred for 1hour (Reaction Solution J2).

A n-butyl lithium hexane solution (2.5 M, 5.0 mL, 12.6 mmol) was slowlyadded dropwise at −30° C. to a diethyl ether (20 mL) solution of1-bromo-2-isopropylbenzene (2.5 g, 12.6 mmol), and the mixed solutionwas stirred for 2 hours at room temperature. The obtained solution wasadded dropwise to Reaction Solution J2 at −78° C., and the mixedsolution was stirred at room temperature for one night. LC-MS Purity:60%. After adding water (50 mL), the resulting solution was made acidic(PH<3) by adding hydrochloric acid, then extracted with methylenechloride (100 mL) and dried over sodium sulfate. Thereafter, the solventwas removed by evaporation, and the residue was recrystallized frommethanol to obtain 1.1 g of the target product as a white product.

1H NMR (CDCl3, ppm/d): 8.34 (t, J=6.0 Hz, 1H), 7.7-7.6 (m, 3H), 7.50 (t,J=6.4 Hz, 1H), 7.39 (m, 1H), 7.23 (m, 1H), 7.1-6.9 (m, 5H), 3.75 (s,3H), 3.05 (m, 1H), 1.15 (d, J=6.8 Hz, 3H), 1.04 (d, J=6.4 Hz, 3H). 31PNMR (CDCl3, ppm/d): −10.5.

(Synthesis Example 11) Synthesis of Ligand (XI)

A n-butyllithium hexane solution (2.5 M, 15.2 mL, 38 mmol) was slowlyadded dropwise to a tetrahydrofuran (40 mL) solution of anhydrousbenzenesulfonic acid (3.0 g, 19 mmol) at 0° C. The mixed solution wasstirred for 1 hour while raising the temperature to room temperature.The reaction solution was cooled to −78° C. and after adding phosphorustrichloride (1.7 mL, 19 mmol), this mixture was stirred for 2 hours(Reaction Solution K1).

Isopropylmagnesium chloride (2.0 M, 9.5 mL, 19 mmol) was slowly addeddropwise at −40° C. to a tetrahydrofuran (40 mL) solution of1-iodo-2,6-dimethoxybenzene (5.0 g, 19 mmol), and the mixture wasstirred for 2 hours at room temperature. The resulting solution wasadded dropwise to Reaction Solution K1 at −78° C., and the mixture wasstirred for 1 hour at room temperature (Reaction Solution K2).

A n-butyl lithium hexane solution (2.5 M, 7.6 mL, 19.0 mmol) was slowlyadded dropwise at −30° C. to a diethyl ether (30 mL) solution of1-bromo-2-isopropylbenzene (3.8 g, 19.0 mmol), and the mixed solutionwas stirred for 2 hours at room temperature. The obtained solution wasadded dropwise to Reaction Solution K2 at −78° C., and the mixedsolution was stirred at room temperature for one night. LC-MS Purity:39%. After adding water (60 mL), the resulting solution was made acidic(PH<1) by adding hydrochloric acid, then extracted with methylenechloride (100 mL×3) and dried over sodium sulfate. Thereafter, thesolvent was removed by evaporation, and the residue was recrystallizedfrom methanol to obtain 4.4 g of the target product as a white product.

1H NMR (CDCl3, ppm/d): 9.67 (d, J=290.2 Hz, 111), 8.34 (m, 1H), 7.7-7.5(m, 3H), 7.50 (m, 1H), 7.41 (m, 1H), 7.33-7.26 (m, 3H), 6.67 (dd, J=5.2,8.8 Hz, 2H), 3.65 (s, 6H), 2.97 (m, 1H), 1.14 (d, J=6.8 Hz, 3H), 1.05(d, J=6.4 Hz, 3H). 31P NMR (CDCl3, ppm/d): −19.1.

(Synthesis Example 12) Synthesis of Complex (XII)

Sodium carbonate (0.19 g, 1.75 mmol) was added to a methylene chloride(40 mL) solution of Ligand (I) (0.62 g, 1.45 mmol), and the mixture wasstirred for 4 hours at room temperature. The reaction solution wascooled to −20° C. and after adding Ni(PPh₃)₂(Ph)Cl complex (1.0 g, 1.46mmol), this mixture was stirred at room temperature for one night.Thereafter, the solvent was removed by evaporation, and the residue wasextracted with diethyl ether (10 mL×3) and then recrystallized to obtain0.9 g of the objective complex.

1H NMR (CDCl3, ppm/d): 8.45-7.07 (m, 32H), 2.29 (m, 2H), 1.24 (m, 12H).31P NMR (CDCl3, ppm/d): −9.5.

(Synthesis Example 13) Synthesis of Ligand (XIII)

A n-butyllithium hexane solution (2.5 M, 25 mL, 62 mmol) was slowlyadded dropwise to a tetrahydrofuran (60 mL) solution of anhydrousbenzenesulfonic acid (5.2 g, 32.9 mmol) at 0° C. The mixed solution wasstirred for 20 hours while raising the temperature to room temperature.To this reaction solution, a tetrahydrofuran (20 mL) solution ofbis(2-methoxyphenyl)methoxyphosphine (9.1 g, 32.9 mmol) was addeddropwise, and the resulting solution was stirred for 16 hours. Afteradding ammonium chloride (3.4 g, 62 mmol), the solvent was removed byevaporation, and the residue was added with water (100 mL), then washedwith MTBE (40 mL×2), made acidic (PH<3) by adding hydrochloric acid,extracted with methylene chloride (60 mL×2), dried over sodium sulfate,and recrystallized at −35° C. to obtain 3.7 g of the target product as awhite product.

1H NMR (C2D2Cl4, ppm/d): 6.7-8.2 (m, 12H), 3.79 (s, 6H). 31P NMR(C2D2C14, ppm/d): −9.8.

(Synthesis Example 14) Synthesis of Ligand (XIV)

A n-butyllithium hexane solution (2.5 M, 3.8 mL, 9.4 mmol) was slowlyadded dropwise to a tetrahydrofuran (20 mL) solution of anhydrousbenzenesulfonic acid (0.74 g, 4.7 mmol) at 0° C. The mixed solution wasstirred for 2 hours while raising the temperature to room temperature.The reaction solution was cooled to −78° C. and after adding phosphorustrichloride (0.41 mL, 4.7 mmol), this mixture was stirred for 2 hours atroom temperature (Reaction Solution L).

A tert-butyllithium hexane solution (1.5 M, 12.5 mL, 18.8 mmol) wasslowly added dropwise at 0° C. to a tetrahydrofuran (25 mL) solution of1-bromo-2-(2′,6′-dimethoxyphenyl)benzene (2.8 g, 9.4 mmol), and themixed solution was stirred for 30 minutes. The obtained solution wasadded dropwise to Reaction Solution L at −50° C., and the mixed solutionwas stirred at room temperature for one night. After removing thesolvent by evaporation, water (200 mL) was added, and the resultingsolution was made acidic (PH<3) by adding hydrochloric acid, extractedwith MTBE (100 mL×3) and dried over sodium sulfate. Thereafter, thesolvent was removed by evaporation, and the residue was washed with THF(5 mL) to obtain 0.5 g of the target product as a white product.

1H NMR (CDCl3, ppm/d): 8.08 (m, 1H), 7.61 (m, 3H), 7.42-7.12 (m, 10H),6.68-6.22 (br, 4H), 3.84-3.31 (br, 9H), 2.96 (br, 3H). 31P NMR (CDCl3,ppm/d): −2.4.

3. Preparation of Chemically Treated Montmorillonite

Treatment Example 1 Preparation of Sulfuric Acid/Lithium Sulfate-TreatedMontmorillonite

In a 500 mL-volume three-neck round flask equipped with a stirring bladeand a reflux device, 170 g of distilled water was charged and 50 g of98% sulfuric acid was added dropwise. After setting the internaltemperature to 90° C., 30 g of BENCLAY SL (produced by MizusawaIndustrial Chemicals, Ltd.) was added, and the mixture was stirred.Thereafter, reaction was allowed to proceed at 90° C. for 3.5 hours, andthe obtained slurry was poured in 150 mL of distilled water, therebystopping the reaction, filtered by an apparatus with a Nutsche filterand an aspirator connected to a suction bottle, and washed with 75 mL ofdistilled water. The obtained cake was dispersed in 300 mL of distilledwater and after stirring, filtered. This operation was repeated threetimes.

The recovered cake was added to an aqueous solution prepared bydissolving 17 g of zinc sulfate heptahydrate in 135 mL of pure water ina 1 L-volume beaker and reacted at room temperature for 2 hours, and theobtained slurry was filtered by an apparatus with a Nutsche filter andan aspirator connected to a suction bottle, and washed with 75 mL ofdistilled water. The obtained cake was dispersed in 300 mL of distilledwater and after stirring, filtered. This operation was repeated threetimes.

The cake was dried at 120° C. all night, as a result, 22 g of achemically treated form was obtained. This chemically treatedmontmorillonite was put in a 200 mL-volume flask, dried under reducedpressure at 200° C. and after gas generation was settled, further driedunder reduced pressure for 2 hours. After the drying, this was stored ina nitrogen atmosphere. When used for polymerization evaluation, themontmorillonite was slurried with methylene chloride or toluene (40mg-montmorillonite/ml-solvent) and then added.

Treatment Example 2 Organic Aluminum Treatment of Chemically TreatedMontmorillonite

In a flask having an inner volume of 200 mL, 1 g of the dried chemicallytreated montmorillonite obtained above (Treatment Example 1) wasweighed, and 3.6 mL of heptane and 6.4 mL (2.5 mmol) of a heptanesolution of triisobutylaluminum were added. This mixture was stirred atroom temperature for 1 hour, and the resulting solution was washed withmethylene chloride and toluene until a residual liquid ratio of 1/100.The slurry amount was then adjusted to 25 mL by using the same solventas that finally used for washing.

4. Polymerization

(1) Examples 1-1 to 1-11 and Comparative Examples 1-1 and 1-2

In a 30 ml-volume flask thoroughly purged with nitrogen, 100 micromol ofbis(benzylideneacetone) palladium and phosphorus-sulfonic acid wereweighed and dehydrated toluene (10 mL) was added. The mixture wastreated by an ultrasonic vibrator for 10 minutes to prepare a catalystslurry. Subsequently, a 1000 mL stainless steel autoclave reactorequipped with an induction stirring was purged with purified nitrogen,and purified toluene (617 mL) and methyl acrylate (72 mL, adjusted tohave a concentration of 1 mol/L at the polymerization) were introducedinto the autoclave in a purified nitrogen atmosphere. The catalystsolution prepared above was added thereto, and polymerization wasstarted at room temperature under an ethylene pressure of 3 MPa. Thetemperature was kept at 80° C. during the reaction, and ethylene wascontinuously supplied to maintain the partial pressure of ethylene at 3MPa.

After the polymerization, the ethylene was purged, and the autoclave wascooled to room temperature. In the case where the obtained polymer was atoluene-insoluble solid, the polymer and the solvent were separated byfiltration. When the separation by filtration was insufficient, thepolymer was reprecipitated using ethanol (1 L), and the precipitatedpolymer was filtered. Furthermore, the obtained solid polymer wasdispersed in ethanol (1 L), and 1 N-hydrochloric acid (20 ml) was addedthereto. This mixture was stirred for 60 minutes, and the polymer wasfiltered. The obtained solid polymer was washed with ethanol and driedunder reduced pressure at 60° C. for 3 hours, whereby the polymer wasfinally recovered. The results of each polymerization are shown in Table2.

TABLE 2 Comonomer Activity M_(w) M_(w)/M_(n) Tm Content^(a) MFR, MI RUNComplex Ligand g/mol/hr ×10³ — ° C. Mol % (2 Kg) (10 Kg) Example 1-1 —(I) 8.6E+05 153 2.4 118.9 0.9 0.15 1.11 Example 1-2 — (II) 3.5E+06 941.9 123.6 0.8 1.00 8.34 Example 1-3 — (III) 9.0E+05 160 1.9 120.6 1.00.11 0.98 Example 1-4 — (IV) 1.8E+06 168 2.1 120.4 1.0 0.16 1.10 Example1-5 — (V) 1.7E+03 54 2.0 117.5 1.4 14.86  — Example 1-6 — (VII) 1.1E+06118 2.2 117.7 0.8 0.69 4.07 Example 1-7 — (VIII) 2.9E+06 143 2.1 123.80.4 0.32 1.85 Example 1-8 — (IX) 1.2E+06 119 2.0 120.2 1.3 0.77 5.11Example 1-9 — (X) 1.4E+06 66 1.9 115.7 1.3 7.03 35.56  Example 1-10 —(XI) 2.6E+06 40 2.0 113.3 1.6 51.00  High Example 1-11 (XII) — 1.4E+0436 6.7 119.7 1.0 — — Comparative — (XIII) 4.2E+05 14 2.0 104.2 2.9 High— Example 1-1 Comparative — (XIV) 6.2E+05 199 2.2 128.9 0.1 0.05 0.42Example 1-2 Conditions: Pd(dba)2/Ligand = 1; Catalyst, 100 μmol;Ethylene Pressure, 3 Mpa; MA, 1M; Toluene; 80° C. ^(a)Estimated by IR.

(2) Example 2-1

In a 30 ml-volume flask thoroughly purged with nitrogen, 100 micromol ofNickel Complex (VII) was added and after adding dehydrated toluene (10mL), treated by an ultrasonic vibrator for 10 minutes to prepare acatalyst slurry. Subsequently, a 1000 mL stainless steel autoclavereactor equipped with an induction stirring was purged with purifiednitrogen, and purifiedtoluene (617 mL) and methyl acrylate (72 mL,adjusted to have a concentration of 1 mol/L at the polymerization) wereintroduced into the autoclave in a purified nitrogen atmosphere. Thecatalyst solution prepared above was added thereto, and polymerizationwas started at room temperature under an ethylene pressure of 3 MPa. Thetemperature was kept at room temperature during the reaction, andethylene was continuously supplied so that the partial pressure ofethylene could be kept at 3 MPa. After 15 minutes, the ethylene waspurged, and the resulting solution was concentrated by an evaporator.Thereto, 1 N-hydrochloric acid (20 ml) was added and after stirring for60 minutes, and the polymer was filtered. The obtained solid polymer waswashed with ethanol and dried under reduced pressure at 60° C. for 3hours, whereby the product was recovered. 0.3 g, Mw: 36,000, Mw/Mn:6.72, Tm: 120.1° C.

(3) Comparative Example 2-1

In a 30 ml-volume flask thoroughly purged with nitrogen, 1,000 micromolof (biscyclooctadiene)nickel and Phosphorus-Sulfonic Acid Ligand (VIII)were added and after adding dehydrated toluene (10 mL), the mixture wastreated by an ultrasonic vibrator for 10 minutes to prepare a catalystslurry. Subsequently, a 1000 mL stainless steel autoclave reactorequipped with an induction stirring was purged with purified nitrogen,and purified toluene (708 mL) and methyl acrylate (1 mol/L) wereintroduced into the autoclave in a purified nitrogen atmosphere. Thecatalyst slurry was added thereto, and polymerization was started atroom temperature under an ethylene pressure of 3 MPa. The temperaturewas kept at room temperature during the reaction, and ethylene wascontinuously supplied to keep the partial pressure of ethylene at 3 MPa.After 15 minutes, the ethylene was purged, and the resulting solutionwas concentrated by an evaporator. Thereto, 1 N-hydrochloric acid (20ml) was added, and the mixture was stirred for 60 minutes, but nopolymer was obtained.

(4) Examples 3-1 to 3-10 and 4-1 to 4-14 and Comparative Examples 3-1 to3-4

A bis(benzylideneacetone)palladium slurry and a phosphorus-sulfonic acidligand slurry were separately prepared and mixed with an ultrasonicvibrator, and the mixture was stirred at room temperature for 15 minutesto prepare a catalyst slurry at the concentration from 0.0025 to 0.02mol/L. Subsequently, to a 10 mL stainless steel-autoclave reactorequipped with an induction stirring and purged with purified nitrogen,purified toluene and a predetermined amount of comonomer wereintroduced. After raising the temperature and pressurizing the systemwith ethylene to 2 MPa, a predetermined amount of the catalyst slurryprepared above was added, and polymerization was started. Here, thetotal liquid amount was adjusted to become 5 mL during thepolymerization. The temperature was kept constant during the reaction,and ethylene was continuously supplied to keep the partial pressure ofethylene at 2 MPa. After 60 minutes, the unreacted ethylene was purged,and the autoclave was cooled to room temperature. The obtained polymerwas recovered by filtration and dried under reduced pressure at 40° C.for 6 hours. Detailed polymerization conditions and results are shown inTables 3 and 4.

TABLE 3 Comonomer Metal Ligand Yield Activity Mw Mw/Mn Tm Content^(a)μmol μmol g g/mol/hr ×10³ — ° C. Mol % Example 3-1 Pd(dba)2 2 (I) 20.362 1.8E+05 94 1.7 117.8 1.5 Example 3-2 Pd(dba)2 1 (I) 0.5 0.3998.0E+05 145 1.6 117.5 2.2 Example 3-3 Pd(dba)2 4 (II) 2 0.636 3.2E+05 651.4 120.1 2.4 Example 3-4 Pd(dba)2 4 (III) 2 0.455 2.3E+05 107 1.5 117.82.4 Example 3-5 Pd(dba)2 2 (IV) 1 0.544 5.4E+05 137 1.6 121.4 3.7Example 3-6 Pd(dba)2 1 (V) 1 0.131 1.3E+05 56 1.8 119.5 1.2 Example 3-7Pd(dba)2 2 (VII) 1 0.716 7.2E+05 117 1.4 125.0 Example 3-8 Pd(dba)2 1(VIII) 0.5 0.126 2.5E+05 99 1.4 123.4 Example 3-9 Pd(dba)2 4 (IX) 20.644 3.2E+05 95 1.5 119.8 Example 3-10 Pd(dba)2 2 (X) 1 0.527 5.3E+0557 1.3 111.9 Example 3-11 Pd(dba)2 2 (XI) 1 0.434 4.3E+05 53 1.3 118.3Comparative Pd(dba)2 4 (XIII) 4 0.214 5.4E+04 10 1.6 99.0 4.4 Example3-1 Comparative Pd(dba)2 4 (XIII) 2 0.093 4.7E+04 NES NES 97.1 NESExample 3-2 Comparative Pd(dba)2 4 (XIV) 4 0.100 2.5E+04 144 1.7 128.00.5 Example 3-3 Comparative Pd(dba)2 4 (XIV) 2 0.406 1.0E+05 118 1.8126.2 0.9 Example 3-4 Conditions: Ethylene Pressure, 2 Mpa; MA, 6 mmol;Toluene; 80° C.; 60 min; NES (Not Enough Sample). ^(a)Estimated by IR.

TABLE 4 Comonomer Metal Ligand Comonomer Yield Activity Content^(a) MwMw/Mn Tm μmol μmol mmol mmol Temp g g/mol/hr mol % ×10³ — ° C. Example4-1 Pd(dba)2 4 (I) 4 tBA 6 — — 80 0.30 7.5E+04 1.4 75.5 1.7 116.5Example 4-2 Pd(dba)2 16 (I) 16 VA 6 — — 80 0.20 1.3E+04 0.2 34.0 1.6132.5 Example 4-3 Pd(dba)2 16 (I) 16 AA 6 — — 80 0.84 5.3E+04 2.1 31.81.5 123.0 Example 4-4 Pd(dba)2 4 (I) 2 MA 6 — — 150 0.14 6.8E+04 1.411.7 1.6 113.8 Example 4-5 Pd(dba)2 8 (I) 4 MA 56 — — 80 0.29 7.3E+047.2 53.9 1.6 90.3 Example 4-6 Pd(dba)2 2 (I) 1 Hexene 6 — — 80 0.525.2E+05 52.1 1.8 120.4 Example 4-7 Pd(dba)2 2 (I) 1 MA 6 Hexene 6 800.06 6.0E+04 2.1(MA), 108.0 1.6 114.0 0.9(Hexene) Example 4-8 Pd(dba)2 1(I) 0.5 LUA 6 — — 80 0.58 1.2E+06 125.4 1.4 112.1 Example 4-9 Pd(dba)216 (I) 8 HEA 6 — — 80 1.35 1.7E+05 43.7 1.3 119.4 Example 4-10 Pd(dba)21 (I) 0.5 EUA 6 — — 80 0.12 2.4E+05 48.3 1.3 121.3 Example 4-11 Pd(dba)24 (I) 2 NBMOH 6 — — 80 0.73 3.7E+05 71.8 1.5 122.3 Example 4-12 Pd(dba)22 (I) 1 NBYA 6 — — 80 0.60 6.0E+05 67.2 1.4 112.2 Example 4-13 Pd(dba)24 (I) 2 ATMS 6 — — 80 0.25 1.3E+05 48.2 1.3 127.8 Example 4-14 Pd(dba)24 (I) 2 BTOH 6 — — 80 0.14 3.5E+04 24.1 1.4 128.5 Conditions: EthylenePressure, 2 Mpa; Toluene; 80° C.; 60 min. ^(a)Estimated by IR.

(5) Examples 5-1 to 5-12, 6-1 to 6-4, 7-1 to 7-12 and ComparativeExamples 5-1 and 5-2

To a 10 mL stainless steel-autoclave reactor equipped with an inductionstirring and purged with purified nitrogen, purified toluene and apredetermined amount of comonomer were introduced. After raising thetemperature, the system was pressured with ethylene to 2 MPa. A toluenesolution of (biscyclooctadiene)nickel and a toluene solution ofphosphorus-sulfonic acid ligand were separately prepared and added eachin a predetermined amount in the order of (biscyclooctadiene)nickel andphosphorus-sulfonic acid ligand, and the polymerization was started. Inthe case of using a third component such as aniline, this component wasadded after the addition of (biscyclooctadiene)nickel but before addingthe phosphorus-sulfonic acid ligand. Here, the total liquid amount wasadjusted to become 5 mL during the polymerization. The temperature waskept constant during the reaction, and ethylene was continuouslysupplied to keep the partial pressure of ethylene at 2 MPa. After 60minutes, the unreacted ethylene was purged, and the autoclave was cooledto room temperature. After removing the solvent by evaporation, theresidue was washed suing a small amount of acetone, and the polymer wasrecovered by filtration and dried under reduced pressure at 40° C. for 6hours. The polymerization conditions and results are shown in Tables 5,6 and 7 below.

TABLE 5 Comonomer Ligand Comonomer Yield Activity Mw Mw/Mn TmContent^(a) μmol mmol g g/mol/hr ×10³ — ° C. mol % Example 5-1 (I) 16 MA2 1.15 7.2E+04 12.8 1.7 127.4 0.4 Example 5-2 (I) 16 tBA 2 0.42 2.6E+049.2 1.7 126.2 1.0 Example 5-3 (I) 8 tBA 0.5 0.63 7.9E+04 27.2 1.5 130.50.3 Example 5-4 (III) 16 MA 2 0.04 2.4E+03 NES NES 123.8 2.1 Example 5-5(III) 16 tBA 2 0.35 2.2E+04 8.6 1.9 126.1 1.1 Example 5-6 (III) 16 EA 20.07 4.4E+03 6.1 1.6 124.5 1.4 Example 5-7 (III) 16 AA 2 0.02 1.3E+03NES NES NES NES Example 5-8 (III) 8 tBA 0.5 0.63 7.9E+04 26.4 1.4 130.20.3 Example 5-9 (IV) 8 tBA 0.5 0.32 4.0E+04 25.5 1.6 129.8 0.5 Example5-10 (VI) 16 tBA 2 0.02 1.0E+03 21.8 2.4 121.5 NES Example 5-11 (VII) 16tBA 0.5 0.71 4.5E+04 15.2 1.5 128.7 0.6 Example 5-12 (VIII) 16 tBA 0.51.24 7.8E+04 22.3 1.7 128.4 0.3 Comparative (XIII) 16 tBA 0.5 0.074.1E+03 NES NES NES NES Example 5-1 Comparative (XIV) 8 tBA 0.5 0.516.4E+04 9.5 1.5 112.2 0.1 Example 5-2 Conditions: Ni(cod)2/Ligand = 1;Ethylene Pressure, 2 Mpa; Toluene; 40° C.; 60 min; NES (Not EnoughSample). ^(a)Estimated by IR.

TABLE 6 Comonomer Complex Ligand Comonomer 3rd Component Yield ActivityMw/Mn Tm Content^(a) μmol μmol mmol Temp ° C. mmol g g/mol/hr Mw ×10³ —° C. mol % Example 6-1 — — (I) 16 MA 2 60 Aniline 8 0.087 5.4E+03 4.91.7 125.2 1.2 Example 6-2 — — (III) 16 MA 2 60 MMA 8 0.041 2.6E+03 6.41.8 124.9 2.2 Example 6-3 — — (III) 16 MA 2 60 clay 10 mg 0.054 3.4E+035.9 1.7 124.6 Example 6-4 (XI) 8 — — tBA 2 40 TPB 1 0.057 7.1E+03 NESNES 114.7 0.9 Conditions: Ni(cod)2/Ligand = 1; Ethylene Pressure, 2 Mpa;Toluene; 60 min; NES (Not Enough Sample). ^(a)Estimated by IR.

TABLE 7 Complex Ligand Temp Yield Activity Mw Mw/Mn Tm μmol μmol ° C. gg/mol/hr ×10³ — ° C. Example 7-1 — — (I) 4 60 1.21 3.0E+05 22.3 2.0125.6 Example 7-2 — — (I) 8 40 1.06 1.3E+05 45.1 1.9 123.9 Example 7-3 —— (III) 2 40 0.76 3.8E+05 47.6 1.6 127.5 Example 7-4 — — (IV) 4 40 1.152.9E+05 27.2 1.7 125.2 Example 7-5 — — (V) 4 60 0.32 7.9E+04 2.0 1.5104.4 Example 7-6 — — (VI) 4 60 0.94 2.4E+05 5.2 2.1 126.6 Example 7-7 —— (VII) 4 40 0.95 2.4E+05 33.9 1.7 127.9 Example 7-8 — — (VIII) 4 401.53 3.8E+05 15.9 1.8 120.5 Example 7-9 — — (IX) 2 40 1.32 6.6E+05 51.41.7 130.4 Example 7-10 — — (X) 4 40 1.25 3.1E+05 8.9 1.4 119.6 Example7-11 — — (XI) 4 40 1.00 2.5E+05 33.4 1.8 122.4 Example 7-12 (XII) 2 — —40 0.58 2.9E+05 4.0 1.3 110.1 Conditions: Ni(cod)2/Ligand = 1; EthylenePressure, 2 Mpa; Toluene; 60 min.

(6) Examples 8-1, 8-2, 9-1 and 9-2

A methylene chloride solution or slurry of(bisbenzylideneacetone)palladium and a methylene chloride solution orslurry of phosphorus-sulfonic acid ligand were separately prepared andmixed at room temperature, and the mixture was by an ultrasonic vibratorfor 30 minutes to prepare a catalyst slurry at the concentration from0.0025 to 0.02 mol/L. Thereafter, a predetermined amount of a methylenechloride slurry (40 mg-clay/ml-toluene) of the chemically treatedmontmorillonite, which was obtained in Treatment Example 1 or TreatmentExample 2, was added to the catalyst slurry and further stirred at roomtemperature for 30 minutes to obtain a supported catalyst slurry. Thepolymerization evaluation was performed for a case where the supportedcatalyst slurry obtained here was directly used in the polymerizationevaluation and for a case where the slurry was washed with methylenechloride to a residual liquid ratio of 1/100 and then used.

The 10 mL stainless steel-autoclave reactor equipped with an inductionstirring was purged with purified nitrogen, and purified toluene and apredetermined amount of comonomer were introduced. After raising thetemperature and then pressurizing the system with ethylene to 2 MPa, apredetermined amount of the supported catalyst slurry prepared above wasadded, and polymerization was started. Here, the total liquid amount wasadjusted to become 5 mL during the polymerization. The temperature waskept at 80° C. during the reaction, and ethylene was continuouslysupplied to keep the partial pressure of ethylene at 2 MPa. After 60minutes, the unreacted ethylene was purged, and the autoclave was cooledto room temperature. The obtained polymer was recovered by filtrationand dried under reduced pressure at 40° C. for 6 hours. Detailedpolymerization conditions and results are shown in Table 8.

(7) Examples 10-1 to 10-3, 11-1 and 11-2 and Comparative Examples 11-1and 11-2

A toluene solution or slurry of (biscyclooctadiene)nickel and a toluenesolution or slurry of phosphorus-sulfonic acid ligand were separatelyprepared and mixed using an ultrasonic vibrator for 30 minutes at roomtemperature to prepare a catalyst slurry at the concentration from0.0025 to 0.02 mol/L. Thereafter, a predetermined amount of a tolueneslurry (40 mg-clay/ml-toluene) of the chemically treated clay, which wasobtained in Treatment Example 1 or Treatment Example 2 of ChemicallyTreated Montmorillonite was added to the catalyst slurry and furtherstirred at room temperature for 30 minutes to obtain a supportedcatalyst slurry. The polymerization evaluation was performed for a casewhere the supported catalyst slurry obtained here was directly used inthe polymerization evaluation and for a case where the slurry was washedwith toluene to a residual liquid ratio of 1/100 and then used.

The 10 mL stainless steel-autoclave reactor equipped with an inductionstirring was purged with purified nitrogen, purified toluene and apredetermined amount of comonomer were introduced. After raising thetemperature and then pressurizing the system with ethylene to 2 MPa, apredetermined amount of the supported catalyst slurry prepared above wasadded, and polymerization was started. Here, the total liquid amount wasadjusted to become 5 mL during the polymerization. The temperature waskept at 80° C. during the reaction, and ethylene was continuouslysupplied to keep the partial pressure of ethylene at 2 MPa. After 60minutes, the unreacted ethylene was purged, and the autoclave was cooledto room temperature. The obtained polymer was recovered by filtrationand dried under reduced pressure at 40° C. for 6 hours. Detailedpolymerization conditions and results are shown in Table 9.

TABLE 8 Clay Washing Comonomer Ligand Treatment of Catalyst ComonomerYield Activity Content^(a) Mw Mw/Mn Tm μmol Example mg Component mmol gg/mol/hr mol % ×10³ — ° C. Example 8-1 (I) 2 (1) 10 none — — 0.804.0E+05 — 106.9 1.5 132.1 Example 8-2 (I) 2 (1) 10 none MA 6 0.231.1E+05 1.9 126.1 1.4 113.3 Example 9-1 (I) 2 (2) 10 none — — 0.462.3E+05 — 96.0 1.4 132.2 Example 9-2 (I) 2 (2) 10 none 6 0.20 1.0E+052.0 110.4 1.4 118.9 Conditions: Pd(dba)2/Ligand = 1; Ethylene Pressure,2 MPa; Time, 60 min; Toluene; 80° C.; ^(a)Estimated by IR.

TABLE 9 Clay Washing Comonomer Ligand Treatment of Catalyst ComonomerYield Activity Content^(a) Mw Mw/Mn μmol Example mg Component mmol gg/mol/hr mol % ×10³ — Example 10-1 (IV) 2 (1) 10 none — — 1.61 8.0E+05 —12.3 1.6 Example 10-2 (IV) 4 (1) 20 none tBA 0.5 0.03 6.8E+03 0.2 16.91.8 Example 10-3 (IV) 2 (1) 10 washed — — 0.68 6.8E+05 — 15.0 1.5Example 11-1 (IV) 2 (2) 10 none — — 1.59 8.0E+05 — 17.9 1.2 Example 11-2(IV) 4 (2) 20 none tBA 0.5 0.05 1.2E+04 NES 12.0 1.6 Example 11-3 (IV) 2(2) 10 washed — — 0.93 4.6E+05 — 15.4 1.5 Comparative (XII) 2 (2) 10none — — 0.03 1.3E+04 — NES NES Example 11-1 Comparative (XII) 2 (2) 10washed — — 0.01 6.0E+03 — NES NES Example 11-2 Conditions:Ni(cod)2/Ligand = 1; Ethylene Pressure, 2 MPa; Time, 60 min; Toluene;80° C.; NES (not Enough Sample). ^(a)Estimated by IR.

(8) Example 12: Copolymerization of Ethylene/1-Hexene/Ethyl Acrylate

In a 30 ml-volume flask thoroughly purged with nitrogen, 200 micromol ofbis(benzylideneacetone)palladium and Phosphorus-Sulfonic Acid Ligand (I)were weighed and dehydrated toluene (10 mL) was added. The mixture wastreated by an ultrasonic vibrator for 10 minutes to prepare a catalystslurry. Subsequently, To a 1000 mL stainless steel autoclave reactorequipped with an induction stirring and purged with purified nitrogen,toluene (170 mL), 1-hexene (279 mL) and ethyl acrylate (245 mL) wereintroduced in a purified nitrogen atmosphere. The entire amount of thecatalyst slurry prepared above was added thereto, and polymerization wasstarted by pressurizing the system with ethylene to 3 MPa. Thetemperature was kept at 80° C. during the reaction, and ethylene wascontinuously supplied to maintain the pressure of ethylene at 3 MPa.After 180 minutes, the ethylene was purged, and the autoclave was cooledto room temperature. The polymer was reprecipitated using ethanol (1 L)and the precipitated polymer was filtered. Furthermore, the obtainedsolid polymer was dispersed in ethanol (1 L), and 1 N-hydrochloric acid(20 ml) was added thereto. This mixture was stirred for 60 minutes, andthe polymer was filtered. The obtained solid polymer was washed withethanol and dried under reduced pressure at 60° C. for 3 hours, wherebythe polymer was finally recovered.

Here, 74 g of an ethylene/1-hexene/ethyl acrylate copolymer wasobtained. The catalytic activity was 1.2E+05 g/mol/h, Mw by GPC was92,000, Mw/Mn was 2.1, the melting point was 102.9° C., and the monomerincorporation was an ethylene content of 96.3 mol %, a 1-hexene contentof 1.1 mol %, and an ethyl acrylate content of 2.6 mol % (13C NMR). Thepolymerization conditions and results are shown in Tables 10 and 11.

(9) Examples 13 to 22: Copolymerization of Ethylene/1-Hexene/EthylAcrylate

In a 30 ml-volume flask thoroughly purged with nitrogen, palladiumbisbenzylideneacetone and Phosphorus-Sulfonic Acid Ligand (I) wereweighed each in the predetermined amount shown in Table 10 and afteradding dehydrated toluene (10 mL), the mixture was treated by anultrasonic vibrator for 10 minutes to prepare a catalyst slurry.Subsequently, the inside of an induction stirring-type stainlesssteel-made autoclave having an inner volume of 2.4 liter was purged withpurified nitrogen, and purified toluene (in Example 22, hexane was usedin place of toluene), ethyl acrylate and 1-hexene each in thepredetermined amount shown in Table 10 were introduced into theautoclave.

The inside of the autoclave was controlled to a predetermined amount andthe pressure in the autoclave was raised to 0.1 MPa by nitrogen.Furthermore, the ethylene partial pressure was raised (totalpressure-ethylene partial pressure+0.1).

After the temperature in the autoclave was stabilized, the catalystslurry prepared above was pressed into the autoclave by a small amountof nitrogen to start polymerization. The temperature was kept at apredetermined temperature during the reaction, and ethylene wascontinuously supplied so that the pressure could be kept at apredetermined pressure.

After the polymerization for a predetermined time, the ethylene waspurged, and the autoclave was cooled to room temperature, therebystopping the polymerization. The produced polymer was washed by addingthe reaction solution to 1 L of acetone and separated by filtration. Theseparated polymer was subjected to acetone washing and filtration andafter repeating this operation twice, dried under reduced pressure at60° C. for 3 hours, whereby the polymer was finally recovered. Theresults of each polymerization are shown in Table 11.

TABLE 10 Cat. Solvent EA 1-Hexene Ethylene Press. Temp. Time μmol ml mlmol/l ml mol/l MPa ° C. min Example 12 200 Toluene 170 245 3.2 279 3.23.0 80 180 Example 13 100 Toluene 640 110 1.0 250 2.0 2.0 80 90 Example14 300 Toluene 300 500 5.1 100 0.9 2.0 80 240 Example 15 200 Toluene 260390 4.0 250 2.2 2.0 80 240 Example 16 200 Toluene 540 110 1.1 250 2.22.0 70 60 Example 17 200 Toluene 690 60 0.6 150 1.3 1.5 90 60 Example 18100 Toluene 540 60 0.6 300 2.7 1.5 90 60 Example 19 100 Toluene 500 600.6 340 3.0 2.0 90 60 Example 20 200 Toluene 150 350 3.6 400 3.5 3.0 60240 Example 21 200 Toluene 100 300 3.1 500 4.4 2.0 60 240 Example 22 200n-Hexane 100 300 3.1 500 4.4 2.0 60 240 Conditions: Pd(dba)2/(Ligand(I)) = 1

TABLE 11 Yield Activity MFR FR Mw Mw/Mn d Tm EA Content 1-Hexene ContentRUN g g/mol/h g/10 min — 10⁻⁴ — g/cm³ ° C. mol %^(a) mol %^(a) Example12 74 1.2E+05 1.9 6.4 9.2 2.1 0.9328 102.9 2.6 1.1 Example 13 38 2.6E+050.8 5.3 12.5 1.8 0.9246 111.2 1.2 0.9 Example 14 49 4.1E+04 3.2 5.3 8.62.0 0.9344 95.7 4.5 0.4 Example 15 37 4.7E+04 3.8 5.3 8.4 2.0 0.930796.0 3.8 0.9 Example 16 60 3.0E+05 0.5 5.8 14.2 1.9 0.9257 112.4 1.1 0.8Example 17 78 3.9E+05 5.2 5.7 7.3 1.8 0.9267 110.0 1.0 1.4 Example 18 454.5E+05 8.7 5.3 7.2 1.8 0.9228 106.1 1.0 1.9 Example 19 47 4.7E+05 5.65.3 7.6 1.9 0.9221 110.7 0.6 1.8 Example 20 42 5.3E+04 0.1 19.2 16.5 3.00.9287 117.6 0.8 0.5 Example 21 31 3.9E+04 0.8 6.8 12.1 2.1 0.9250 105.22.0 1.2 Example 22 23 2.9E+04 1.1 6.4 11.1 2.0 0.9244 104.5 2.3 1.1^(a)Estimated by ¹³C NMR

(10) Example 23: Copolymerization of Ethylene/Propylene/Methyl Acrylate

In a 30 ml-volume flask thoroughly purged with nitrogen, palladiumbisbenzylideneacetone and Phosphorus-Sulfonic Acid Ligand (I) wereweighed each in an amount of 100 micromol and after adding dehydratedtoluene (10 mL), the mixture was treated by an ultrasonic vibrator for10 minutes to prepare a catalyst slurry. Subsequently, a 1000 mLstainless steel autoclave reactor equipped with an induction stirringwas purged with purified nitrogen, and purified toluene (617 mL) andmethyl acrylate (72 mL, adjusted to have a concentration of 1 mol/L atthe polymerization) were introduced into the autoclave in a purifiednitrogen atmosphere. The entire amount of the catalyst slurry preparedabove was added thereto, and polymerization was started by pressurizingthe system to a pressure of 1.0 MPa with an ethylene/propylene mixed gas(gas compositional ratio: 7/3) previously adjusted to 80° C. by using aseparate autoclave. The temperature was kept at 80° C. during thereaction, and the mixed gas was continuously supplied so that thepressure could be kept at 1.0 MPa. After 60 minutes, the mixed gas waspurged, and the autoclave was cooled to room temperature. The polymerwas reprecipitated using ethanol (1 L), and the precipitated polymer wasfiltered. Furthermore, the obtained solid polymer was dispersed inethanol (1 L), and 1 N-hydrochloric acid (20 ml) was added thereto. Thismixture was stirred for 60 minutes, and the polymer was filtered. Theobtained solid polymer was washed with ethanol and dried under reducedpressure at 60° C. for 3 hours, whereby 7.0 g of anethylene/propylene/ethyl acrylate copolymer was finally recovered. Thecatalytic activity was 6.6E+04 g/mol/h. The molecular weight Mw of theobtained copolymer was 65,000, Mw/Mn was 1.9, the melting point was92.1° C., the methyl acrylate content was 3.7 mol %, and the propylenecontent was 2.4 mol %. The polymerization results are shown in Table 12.

(11) Example 24: Copolymerization of Ethylene/Propylene/Methyl Acrylate

In a 30 ml-volume flask thoroughly purged with nitrogen, palladiumbisbenzylideneacetone and Phosphorus-Sulfonic Acid Ligand (I) wereweighed each in an amount of 264 micromol and after adding dehydratedtoluene (20 mL), the mixture was treated by an ultrasonic vibrator for10 minutes to prepare a catalyst slurry.

A separate 2 L-volume induction stirring-type autoclave was previouslyprepared as a buffer tank for an ethylene/propylene mixed gas. Liquefiedpropylene (150 mL) and ethylene (2.5 MPa) were charged into this tank at20° C. and stirred until these were thoroughly mixed and then, thetemperature was raised to 50° C.

Subsequently, the inside of an induction stirring-type stainlesssteel-made autoclave having an inner volume of 2 liters for use in thepolymerization was purged with purified nitrogen, and purified toluene(500 mL), methyl acrylate (37.5 mL) and the entire amount of thecatalyst slurry prepared above were introduced into the autoclave in apurified nitrogen atmosphere. Propylene (100 mL) was introduced into theautoclave at 20° C., and the mixed gas prepared above was introduced toraise the pressure to 1.2 MPa. Thereafter, the temperature was raised to70° C., and the mixed gas was added so that the total pressure couldbecome 2.0 MPa. The mixed gas was appropriately introduced to keep thetotal pressure during the polymerization. After 10 minutes, ethanol (25ml) was charged, and the unreacted gas was purged, thereby stopping thepolymerization. The recovered toluene suspension was added with ethanol(1,000 mL), and the mixture was left standing still for one night andthen filtered. Acetone (500 ml) was added to the precipitate and afterstirring at 20° C. for 20 minutes, filtration was performed. Thiswashing was performed two more times. After the washing, the polymer wasdried under reduced pressure at 70° C. for 3 hours to obtain 23.2 g ofan ethylene-propylene-methyl acrylate copolymer (catalytic activity:5.3E+05 (g/mol/h)). The melting point by DSC of the obtained copolymerwas 107.2° C., Mw by GPC was 80,000, Mw/Mn was 1.7, the methyl acrylatecontent was 1.0 mol %, and the propylene content was 3.0 mol %. Thepolymerization results are shown in Table 12.

(12) Example 25: Copolymerization of Ethylene/Propylene/Methyl Acrylate

In a 100 ml-volume flask thoroughly purged with nitrogen, palladiumbisbenzylideneacetone and Phosphorus-Sulfonic Acid Ligand (I) wereweighed each in an amount of 580 micromol and after adding dehydratedtoluene (50 mL), the mixture was treated by an ultrasonic vibrator for10 minutes to prepare a catalyst slurry.

A separate 2 L-volume induction stirring-type autoclave was previouslyprepared as a buffer tank for an ethylene/propylene mixed gas. Liquefiedpropylene (150 mL) and ethylene (2.5 MPa) were charged into this tank at20° C. and stirred until these were thoroughly mixed and then, thetemperature was raised to 50° C.

Subsequently, the inside of an induction stirring-type stainlesssteel-made autoclave having an inner volume of 2 liters for use in thepolymerization was purged with purified nitrogen, and purified toluene(500 mL), methyl acrylate (37.5 mL) and the entire amount of thecatalyst slurry prepared above were introduced into the autoclave in apurified nitrogen atmosphere. Propylene (100 mL) was introduced into theautoclave at 20° C., and the mixed gas prepared above was introduced toraise the pressure to 1.2 MPa. Thereafter, the temperature was raised to55° C., and the mixed gas was added so that the total pressure couldbecome 2.0 MPa. The mixed gas was appropriately introduced to keep thetotal pressure during the polymerization. After 25 minutes, ethanol (25ml) was charged, and the unreacted gas was purged, thereby stopping thepolymerization. The recovered toluene suspension was added with ethanol(1,000 mL), and the mixture was left standing still for one night andthen filtered. Acetone (500 mL) was added to the precipitate and afterstirring at 20° C. for 20 minutes, filtration was performed. Thiswashing was performed two more times. After the washing, the polymer wasdried under reduced pressure at 70° C. for 3 hours to obtain 19.6 g ofan ethylene-propylene-methyl acrylate copolymer (catalytic activity:8.1E+04 (g/mol/h)). The melting point by DSC of the obtained copolymerwas 113.6° C., Mw by GPC was 58,000, Mw/Mn was 1.6, the methyl acrylatecontent was 0.6 mol %, and the propylene content was 2.4 mol %. Thepolymerization results are shown in Table 12.

(13) Example 26: Copolymerization of Ethylene/Propylene/Methyl Acrylate

In a 50 ml-volume flask thoroughly purged with nitrogen, palladiumbisbenzylideneacetone and Phosphorus-Sulfonic Acid Ligand (I) wereweighed each in an amount of 256 micromol and after adding dehydratedtoluene (20 mL), the mixture was treated by an ultrasonic vibrator for10 minutes to prepare a catalyst slurry.

A separate 2 L-volume induction stirring-type autoclave was previouslyprepared as a buffer tank for an ethylene/propylene mixed gas. Liquefiedpropylene (150 mL) and ethylene (2.5 MPa) were charged into this tank at20° C. and stirred until these were thoroughly mixed and then, thetemperature was raised to 50° C.

Subsequently, the inside of an induction stirring-type stainlesssteel-made autoclave having an inner volume of 2 liters for use in thepolymerization was purged with purified nitrogen, and purified toluene(500 mL), methyl acrylate (46.9 mL) and the entire amount of thecatalyst slurry prepared above were introduced into the autoclave in apurified nitrogen atmosphere. Propylene (100 mL) was introduced into theautoclave at 20° C., and the mixed gas prepared above was introduced toraise the pressure to 1.2 MPa. Thereafter, the temperature was raised to55° C., and the mixed gas was added so that the total pressure couldbecome 2.0 MPa. The mixed gas was appropriately introduced to keep thetotal pressure during the polymerization. After 30 minutes, ethanol (25ml) was charged, and the unreacted gas was purged, thereby stopping thepolymerization. The recovered toluene suspension was added with ethanol(1,000 mL), and the mixture was left standing still for one night andthen filtered. The obtained precipitate was added with toluene (100 mL)and 35% hydrochloric acid (0.5 mL), and the mixture was stirred at 70°C. for 30 minutes and again filtered. Acetone (500 mL) was added to theprecipitate and after stirring at 20° C. for 20 minutes, filtration wasperformed. This washing was performed two more times. After the washing,the polymer was dried under reduced pressure at 70° C. for 3 hours toobtain 1.87 g of an ethylene-propylene-methyl acrylate copolymer(catalytic activity: 1.5E+04 (g/mol/h)). The melting point by DSC of theobtained copolymer was 120.1° C., Mw by GPC was 55,000, Mw/Mn was 1.9,the methyl acrylate content was 0.6 mol %, and the propylene content was1.0 mol %. The polymerization results are shown in Table 12.

TABLE 12 MA Propylene Yield Activity MFR Mw Mw/Mn Tm Content Content RUNg g/mol/h g/10 min 10⁻⁴ — ° C. mol %^(a) mol %^(a) Example 7.0 6.6E+041.9 6.5 1.9 92.1 3.7 2.4 23 Example 23.2 5.3E+05 — 8.0 1.7 107.2 1.0 3.024 Example 19.6 8.1E+04 — 5.8 1.6 113.6 0.6 2.4 25 Example 1.87 1.5E+04— 5.5 1.9 120.1 0.6 1.0 26 ^(a)Estimated by ¹³C NMR

(14) Examples 27 to 29: Ethylene Homopolymerization

In a 30 ml-volume flask thoroughly purged with nitrogen, palladiumbisbenzylideneacetone and phosphorus-sulfonic acid ligand (I) wereweighed each in an amount of 25 micromol by using thephosphorus-sulfonic acid ligand shown in Table 13 and after addingdehydrated toluene (10 mL), the mixture was treated by an ultrasonicvibrator for 10 minutes to prepare a catalyst slurry. Subsequently, a1000 mL stainless steel autoclave reactor equipped with an inductionstirring was purged with purified nitrogen, and purified toluene (790mL) was introduced into the autoclave in a purified nitrogen atmosphere.The entire amount of the catalyst slurry prepared above was added andafter raising the temperature to 80° C., the system was pressurized atan ethylene pressure of 3.0 MPa to start the polymerization. Thetemperature was kept at 80° C. during the reaction, and the mixed gaswas continuously supplied so that the partial pressure could be kept at3.0 MPa. After 60 minutes, the ethylene gas was purged, and theautoclave was cooled to room temperature. The precipitated polymer wasfiltered. Furthermore, the obtained polymer was dispersed in ethanol (1L), and 1 N-hydrochloric acid (20 ml) was added thereto. This mixturewas stirred for 60 minutes, and the polymer was filtered. The obtainedsolid polymer was washed with ethanol and dried under reduced pressureat 60° C. for 3 hours, whereby an ethylene homopolymer was finallyrecovered. The polymerization results are shown in Table 13.

The polyethylene homopolymer of Example 27 was measured by 13C-NMR, as aresult, a short-chain branch such as methyl ethyl was unrecognized andwas below the detection limit, and the homopolymer was confirmed to be apolyethylene with a very small amount of short-chain branches.

TABLE 13 Yield Activity MFR Mw Mw/Mn Tm RUN Ligand g g/mol/h g/10 min FR10⁻⁴ — ° C. Example 27 (I) 41.1 1.6E+06 1.9  21.1 17.4 2.4 135.1 Example28 (III) 18.7 7.5E+05 0.06  8.6 19.0 2.5 137.1 Example 29 (IV) 29.91.8E+06 — — 16.8 2.1 133.8 Conditions: Pd(dba)2/Ligand = 1; Catalyst, 25μmol; Ethylene, 3 MPa; 80° C., 1 h.

(15) Examples 30 and 31: Copolymerization of Ethylene-Ethyl Acrylate

In a 30 ml-volume flask thoroughly purged with nitrogen, palladiumbisbenzylideneacetone and Phosphorus-Sulfonic Acid Ligand (I) wereweighed each in the predetermined amount shown in Table 14 and afteradding dehydrated toluene (10 mL), the mixture was treated by anultrasonic vibrator for 10 minutes to prepare a catalyst slurry.Subsequently, a 1000 mL stainless steel autoclave reactor equipped withan induction stirring was purged with purified nitrogen, and purifiedtoluene and methyl acrylate each in the predetermined amount shown inTable 14 were introduced into the autoclave in a purified nitrogenatmosphere. The catalyst solution prepared above was added thereto, andpolymerization was started at room temperature under an ethylenepressure of 3 MPa. The temperature was kept at 80° C. during thereaction, and ethylene was continuously supplied for a predeterminedtime so that the partial pressure of ethylene could be kept at 3 MPa.

After the completion of polymerization, the ethylene was purged, and theautoclave was cooled to room temperature. In the case where the obtainedpolymer was a toluene-insoluble solid, the polymer and the solvent wereseparated by filtration. When the separation by filtration wasinsufficient, the polymer was reprecipitated using ethanol (1 L), andthe precipitated polymer was filtered. Furthermore, the obtained solidpolymer was dispersed in ethanol (1 L), and 1 N-hydrochloric acid (20ml) was added thereto. This mixture was stirred for 60 minutes, and thepolymer was filtered. The obtained solid polymer was washed with ethanoland dried under reduced pressure at 60° C. for 3 hours, whereby thepolymer was finally recovered. The results of each polymerization areshown in Table 14.

As a result of confirmation by 13C-NMR, ethyl acrylate was inserted inthe main chain, and a short-chain branch such as methyl ethyl could notbe recognized.

TABLE 14 EA Ligand Toluene EA Time Yield Activity MFR Mw Mw/Mn d TmContent RUN μmol mL mL mol/L min g g/mol/h g/10 min FR 10⁻⁴ — g/cm³ ° C.mol %^(a) Example 30 200 445 245 3.0 90 45.6 1.5E+05 0.38 6.91 13.1 2.10.9313 110.2 2.5 Example 31 100 614 76 1.0 60 71.4 7.1E+05 0.29 7.6013.4 2.1 0.9308 118.8 1.3 Conditions: Pd(dba)2/(Ligand(I)) = 1;Catalyst, 25 μmol; Ethylene Pressure, 3 MPa; 80° C. ^(a)Estimated by ¹³CNMR.

(16) Examples 32 and 33: Copolymerization of Ethylene-1-Hexene

In a 30 ml-volume flask thoroughly purged with nitrogen, palladiumbisbenzylideneacetone and Phosphorus-Sulfonic Acid Ligand (I) wereweighed each in the predetermined amount shown in Table 15 and afteradding dehydrated toluene (10 mL), the mixture was treated by anultrasonic vibrator for 10 minutes to prepare a catalyst slurry.Subsequently, a 1000 mL stainless steel autoclave reactor equipped withan induction stirring was purged with purified nitrogen, andpurifiedtoluene and 1-hexene each in the predetermined amount shown inTable 15 were introduced into the autoclave in a purified nitrogenatmosphere. The catalyst solution prepared above was added thereto, andpolymerization was started at room temperature under an ethylenepressure of 3 MPa. The temperature was kept at 80° C. during thereaction, and ethylene was continuously supplied for a predeterminedtime so that the partial pressure of ethylene could be kept at 3 MPa.

After the completion of polymerization, the ethylene was purged, and theautoclave was cooled to room temperature. In the case where the obtainedpolymer was a toluene-insoluble solid, the polymer and the solvent wereseparated by filtration. When the separation by filtration wasinsufficient, the polymer was reprecipitated using ethanol (1 L), andthe precipitated polymer was filtered. Furthermore, the obtained solidpolymer was dispersed in ethanol (1 L), and 1 N-hydrochloric acid (20ml) was added thereto. This mixture was stirred for 60 minutes, and thepolymer was filtered. The obtained solid polymer was washed with ethanoland dried under reduced pressure at 60° C. for 3 hours, whereby thepolymer was finally recovered. The results of each polymerization areshown in Table 15.

TABLE 15 Toluene 1-Hexene Time Yield Activity MFR Mw Mw/Mn Tm d RUN mLmL mol/L min g g/mol/h g/10 min FR 10⁻⁴ — ° C. g/cm³ Example 32 683 170.2 60 26.9 1.1E+05 0.12 6.27 20.4 2.0 132.7 0.9347 Example 33 603 871.0 120 33.9 6.8E+05 0.17 6.45 17.6 2.2 127.6 0.9267 Conditions:Pd(dba)2/Ligand = 1; Catalyst, 25 μmol; Ethylene, 3 MPa; 80° C.

(17) Example 34: Copolymerization of Ethylene/Propylene

Copolymerization was performed in the same manner as in Example 23except for not using methyl acrylate and using 700 mL of purifiedtoluene. As a result, 36 g of a ethylene/propylene copolymer wasrecovered. The catalytic activity was 4.3E+05 g/mol/h. The molecularweight Mw of the obtained copolymer was 23,000, Mw/Mn was 2.3, themelting point was 90.2° C., and the propylene content was 16.9 mol.

(18) Example 35: Polymerization of Propylene

Methylene chloride slurries (0.02 mol/L) ofbis(benzylideneacetone)palladium and Phosphorus-Sulfonic Acid Ligand (I)were separately prepared and after treatment by an ultrasonic vibrator,mixed in a molar ratio of 1:1, and the mixture was stirred at roomtemperature for 15 minutes. Subsequently, the 10 mL stainless autoclavereactor was purged with purified nitrogen, and purified toluene wasintroduced. After raising the temperature to 80° C. and pressurizing thesystem with propylene to 0.5 MPa, 8 μmol of the catalyst slurry preparedabove was added, and polymerization was started. Here, the total liquidamount was adjusted to become 5 mL during the polymerization. Thetemperature was kept constant during the reaction, and propylene wascontinuously supplied so that the partial pressure of propylene could bekept at 0.5 MPa. After 60 minutes, the unreacted propylene was purged,and the autoclave was cooled to room temperature. The entire amount ofthe solvent was removed by evaporation, and the polymer was dried underreduced pressure at 40° C. for 6 hours and recovered. The catalyticactivity was 4.75E+03 g/mol/h. The molecular weight Mw of the obtainedpolymer was 136,000 in terms of polyethylene, and Mw/Mn was 2.7.

(19) Example 36: Copolymerization of Propylene/Methyl Acrylate

Methylene chloride slurries (0.02 mol/L) ofbis(benzylideneacetone)palladium and Phosphorus-Sulfonic Acid Ligand (I)were separately prepared and after treatment by an ultrasonic vibrator,mixed in a molar ratio of 1:1, and the mixture was stirred at roomtemperature for 15 minutes. Subsequently, the 10 mL stainless autoclavereactor was purged with purified nitrogen, and purified toluene andmethyl acrylate (6 mmol) were introduced. After raising the temperatureto 80° C. and pressurizing the system with propylene to 0.5 MPa, 8 μmolof the catalyst slurry prepared above was added, and polymerization wasstarted. Here, the total liquid amount was adjusted to become 5 mLduring the polymerization. The temperature was kept constant during thereaction, and propylene was continuously supplied so that the partialpressure of propylene could be kept at 0.5 MPa. After 60 minutes, theunreacted propylene was purged, and the autoclave was cooled to roomtemperature. The entire amount of the solvent was removed byevaporation, and the polymer was dried under reduced pressure at 40° C.for 6 hours and recovered. The catalytic activity was 3.90E+03 g/mol/h.The molecular weight Mw of the obtained polymer was 194,000 in terms ofpolyethylene, and Mw/Mn was 2.0.

(20) Comparative Example 35

For comparison, evaluations of commercially available metallocenepolyethylene and high pressure-process ethyl acrylate copolymer wereperformed by the same method as in Examples above. The polymers usedwere metallocene LL “KARNEL” KF370 produced by Japan Polyethylene Corp.in Comparative Example 35-1, KF373N of the same product in ComparativeExample 35-2, KF480 of the same product in Comparative Example 35-3,high pressure-process EEA “REXPEARL EEA” A1100 produced by JapanPolyethylene Corp. in Comparative Example 35-4, and A1200 of the sameproduct in Comparative Example 35-5. Incidentally, in ComparativeExamples 35-4 and 35-5, the copolymer at the polymerization is onlyethyl acrylate but since the polymer has methyl, ethyl, butyl and amylbranches which are unavoidably by-produced, the total of theseshort-chain branches was converted into the short-chain branchconcentration [C] based on the main-chain carbon and used forcomparison. The results are shown together in Table 16.

TABLE 16 By- Produced Short-Chain MFR Density Tm Branch [C] [X] [C] +[X] g/10 min g/cm³ Mw Mw/Mn ° C. branches/1000C mol % mol % mol % Comp.KERNEL 3.5 0.905 84,000 2.1 88.0 — 5.8 0.0 5.8 Example KF370 35-1 Comp.KERNEL 3.5 0.913 84,000 2.1 98.5 — 4.8 0.0 4.8 Example KF373N 35-2 Comp.KERNEL 4.0 0.918 74,000 2.7 106.7 — 3.8 0.0 3.8 Example KF480 35-3 Comp.REXPEARL 0.4 0.929 84,000 3.4 101.2  9.5 1.9 3.8 5.7 Example EEA 35-4A1100 Comp. REXPEARL 0.7 0.935 94,000 3.5 94.1 10.0 2.0 6.9 8.9 ExampleEEA 35-5 A1200

(21) Evaluation Results of Physical Properties

Evaluation results of physical properties of obtained samples are shownin Table 17.

TABLE 17 Item 9 Item 10 Item 3 Item 4 Item 5 Item 6 Item 7 Item 8 28 −0.3 * 41 − 0.3 * Item 1 Item 2 Tm [C] + [X] 135 − 6.4 × δ(G * =10{circumflex over ( )}5) T90 − T10 Tw Tw Tw Mw Mw/Mn ° C. Mol % ([C] +[X]) ° ° C. ° C. ° C. ° C. Example 12 92,000 2.1 102.9 3.7 112.9 66.210.7 67.9 7.6 20.6 Example 13 125,000 1.8 111.2 2.1 122.5 71.7 7.4 78.44.5 17.5 Example 14 86,000 2.0 95.7 4.8 104.3 68.3 15.9 56.0 11.2 24.2Example 15 84,000 2.0 96.0 4.6 105.6 68.2 14.9 56.8 11.0 24.0 Example 16142,000 1.9 112.4 1.9 122.8 68.0 7.2 80.9 3.7 16.7 Example 17 72,900 1.8110.0 2.4 119.6 69.7 12.9 74.9 5.5 18.5 Example 18 71,900 1.8 106.1 2.9116.4 68.7 13.4 70.1 7.0 20.0 Example 19 76,200 1.9 110.7 2.4 119.6 68.310.8 75.7 5.3 18.3 Example 20 165,000 2.7 117.6 1.3 126.7 46.9 11.3 85.62.3 15.3 Example 21 120,600 2.1 105.2 3.1 115.2 62.9 16.9 68.9 7.3 20.3Example 22 111,100 2.0 104.5 3.4 113.2 65.9 19.8 66.8 8.0 21.0 Example23 65,000 1.9 92.1 6.1 96.0 Example 24 80,000 1.7 107.2 4.0 109.4 72.911.3 71.1 6.7 19.7 Example 25 58,000 1.6 113.6 3.0 115.8 71.3 12.5 77.24.8 17.8 Example 26 55,000 1.9 120.1 1.6 124.8 7.8 84.8 2.6 15.6 Example27 174,000 2.4 135.1 135.0 Example 30 131,000 2.1 110.2 2.5 119.0 9.576.2 5.1 18.1 Example 31 134,000 2.1 118.8 1.3 126.7 62.5 12.8 85.8 2.315.3 Example 32 204,000 2.0 132.7 0.1 134.4 67.2 2.3 97.7 −1.3 11.7Example 33 176,000 2.2 127.6 0.4 132.4 51.0 2.5 93.9 −0.2 12.8 Example34 23,000 2.3 90.2 16.9 26.8 Comparative 84,000 2.1 88.0 5.8 98.1 63.218.1 59.3 10.2 23.2 Example 35-1 Comparative 84,000 2.1 98.5 4.8 104.263.5 16.9 61.3 9.6 22.6 Example 35-2 Comparative 74,000 2.7 106.7 3.8110.8 64.6 13.2 76.5 5.1 18.1 Example 35-3 Comparative 84,000 3.4 101.25.7 98.8 34.4 33.6 60.6 9.8 22.8 Example 35-4 Comparative 94,000 3.594.1 8.9 78.0 35.3 34.8 49.6 13.1 28.1 Example 35-5 Item 13 Item 12Nominal Item 14 Item 16 Item 11 Tensile Tensile nominal Tensile TensileYield Stress at tensile impact Modulus Stress Break strain at strengthItem 17 18 MPa MPa MPa break kJ/m² Wettability Remarks Example 12 1068.9 33.5 13.5 2046 B As a result of 13C-NMR Example 13 136 11.4 43.512.3 2353 B measurement (lower Example 14 35 6.9 40.7 15.2 1947 Adetection limit: 0.1 Example 15 40 7.2 37.7 14.9 1768 A branches/1,000carbon), no Example 16 142 12.2 46.6 13.1 2261 C branch was detectedexcept Example 17 138 11.6 33.2 13.1 1280 C for branch structuresExample 18 113 10.0 32.8 13.9 1264 C derived from α-olefin and Example19 158 11.9 30.7 11.2 1236 C ((meth)acrylic acid)-based Example 20 27715.0 43.5 13.3 1544 C olefin which are the Example 21 90 9.1 45.5 14.12286 B comonomer. Also, a Example 22 69 8.8 46.3 2147 B ((meth)acrylicacid)-based Example 23 olefin present in the Example 24 131 11.6 Bterminal of molecular chain Example 25 243 15.4 C was not detected.Example 26 Furthermore, a chain Example 27 structure where two or moreExample 30 units of α-olefin or Example 31 ((meth)acrylic acid)-basedExample 32 olefin are continuously Example 33 connected was notdetected. Example 34 Comparative 57 7.8 39.5 13.8 2999 D Example 35-1Comparative 91 9.4 40.1 13.6 2477 D Example 35-2 Comparative 118 11.241.3 14.8 1671 D Example 35-3 Comparative 99 8.1 27.2 14.4 990 A Example35-4 Comparative 33 5.3 19.0 14.3 932 A Example 35-55. Review Results of Examples and Comparative Examples

Example 1 revealed that by using the catalyst composition according tothe present invention, relatively high activity and good balance of boththe comonomer content and the molecular weight can be expressed.

Example 2 revealed that in contrast to the related art where anethylene-acrylate copolymer cannot be obtained, the copolymer can beproduced by using the nickel complex according to the present inventionfor the catalyst.

Example 3 revealed that by using the catalyst composition according tothe present invention, relatively high activity and good balance of boththe comonomer content and the molecular weight compared with ComparativeExamples which are the related art, can be expressed.

Example 4 revealed that by using the catalyst composition according tothe present invention, various comonomers can be made applicable.

Example 5 revealed that by using the phosphorus-sulfonic acid ligandaccording to the present invention in combination with nickel for acatalyst composition, an ethylene/polar group-containing olefincopolymer can be produced.

Example 6 revealed that even when the phosphorus-sulfonic acid ligandaccording to the present invention is used in combination with nickelfor a catalyst composition and aniline, MMA, clay or triphenylborane isadded as the third component, an ethylene/polar group-containing olefincopolymer can be produced.

Example 7 revealed that by using the phosphorus-sulfonic acid ligandaccording to the present invention in combination with nickel for acatalyst composition, an ethylene homopolymer can be produced with highactivity.

Examples 8 and 9 revealed that even when a catalyst carrying thephosphorus-sulfonic acid ligand according to the present invention andpalladium is used, an ethylene polymer and an ethylene-acrylatecopolymer are obtained.

Examples 10 and 11 revealed that even when a catalyst carrying thephosphorus-sulfonic acid ligand according to the present invention andnickel is used, an ethylene polymer can be obtained with higher activitythan in Comparative Examples which are the related art. It is alsorevealed that an ethylene-acrylate copolymer is obtained.

Examples 12 to 22 revealed that thanks to the reaction product of thephosphorus-sulfonic acid ligand and a palladium compound, which is thecatalyst composition of the present invention, anethylene-1-hexene-acrylate ternary copolymer having a narrow molecularweight distribution and a relatively high molecular weight can beproduced. Furthermore, Examples 23 to 26 revealed that anethylene-propylene-methyl acrylate ternary copolymer can be alsoproduced.

Examples 27 to 29 revealed that thanks to the reaction product of thephosphorus-sulfonic acid ligand and a palladium compound, which is thecatalyst composition of the present invention, an ethylene homopolymercan be produced with high activity and the obtained polymer can have ahigh molecular weight and a narrow molecular weight distribution, thatis, a polymer with little difference in branching can be produced.

In Examples 30 to 33, it was confirmed that thanks to the reactionproduct of the phosphorus-sulfonic acid ligand and a palladium compound,which is the catalyst composition of the present invention, similarly toExample-1 and Example 4, copolymerization between ethylene and acrylateor between ethylene and 1-hexene proceeds.

In Example 34, it was confirmed by ¹³C-NMR that thanks to the reactionproduct of the phosphorus-sulfonic acid ligand and a palladium compound,which is the catalyst composition of the present invention,copolymerization between ethylene and propylene proceeds.

Examples 35 and 36 revealed that thanks to the reaction product of thephosphorus-sulfonic acid ligand and a palladium compound, which is thecatalyst composition of the present invention, propylenehomopolymerization and copolymerization of propylene/methyl acrylateproceed.

As a result of physical evaluations, the polymer of Example 14 hasalmost the same elastic modulus and almost the same molecular weight asthe polymer of Comparative Example 35-5, but when these two polymers arecompared, the wettability is almost the same, whereas as for themechanical properties, all of the tensile yield stress, nominal tensilestress at break, nominal tensile strain at break and tensile impactstrength in Example 14 show a higher value than in Comparative Example35-5 and are excellent.

The polymer of Example 18 has almost the same elastic modulus and almostthe same molecular weight as the polymer of Comparative Example 35-3,but when these two polymers are compared, the mechanical properties arealmost the same in all of the tensile yield stress, nominal tensilestress at break and nominal tensile strain at break and while thetensile impact strength shows a relatively high value in ComparativeExample 35-3 and is excellent, the wettability is more excellent inExample 18 than Comparative Example 35-3. Accordingly, the polymer ofExample 18 can be said to have a good balance between the mechanicalproperties and the wettability.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope of the invention.

This application is based on Japanese Patent Application (PatentApplication No. 2008-297411) filed on Nov. 20, 2008, and Japanese PatentApplication (Patent Application No. 2009-025443) filed on Feb. 5, 2009,the contents of which are incorporated herein by way of reference.

INDUSTRIAL APPLICABILITY

By performing copolymerization of an α-olefin in the presence of thecatalyst composition of the present invention, an industrially usefulcopolymer having a high comonomer content and at the same time, having ahigh molecular can be produced. This copolymer is excellent in themechanical and thermal properties and applicable as a useful formedbody. More specifically, the copolymer of the present invention can beapplied to various uses such as film, sheet, adhesive resin, binder andcompatibilizer, by utilizing its good properties in terms of, forexample, coatability, printability, antistatic property, inorganicfiller dispersibility, adhesion to other resins, and compatibilizingability for other resins.

The invention claimed is:
 1. A ternary copolymer of an ethylene, anα-olefin having a carbon number of 3 to 10 and a (meth)acrylic acid orester represented by CH₂═C(R¹⁸)CO₂(R¹⁹), wherein R¹⁸ is a hydrogen atomor an alkyl group having a carbon number of 1 to 10, and R¹⁹ is ahydrogen atom or an alkyl group having a carbon number of 1 to 30, whichmay contain a hydroxyl group, an alkoxy group or an epoxy group on anarbitrary position, the ternary copolymer satisfying the followingrequirements (a) and (b): (a) the ratio Mw/Mn of the weight averagemolecular weight (Mw) to the number average molecular weight (Mn)satisfies the following relationship:1.5≦Mw/Mn≦3 (b) the melting point Tm (° C.), the α-olefin content [C](mol %) and the polar group-containing vinyl monomer content [X] (mol %)from the (meth)acrylic acid or ester satisfy the following relationship:60≦Tm≦135−6.4×([C]+[X]) wherein Tm is a peak temperature of a meltingcurve obtained by the measurement using a differential scanningcalorimeter (DSC), and when a plurality of melting peaks are detected,Tm is the temperature of the maximum peak out of detected peaks.
 2. Theternary copolymer as claimed in claim 1, wherein a phase angle δ(G*=0.1MPa at G*−0.1 MPa) as measured by a rotary rheometer is from 40 to 75°.3. The ternary copolymer as claimed in claim 1, wherein a differenceT90−T10 (° C.) between a temperature T10 (° C.) allowing 10 wt % of thetotal to elute in an integrated elution curve as determined by acontinuous temperature rising elution fractionation method (TREF) and atemperature T90 (° C.) allowing 90 wt % of the total to elute, and aweight average elution temperature Tw (° C.) satisfy the followingrelationship:28−0.3×Tw≦T90−T10≦41−0.3×Tw.
 4. The ternary copolymer as claimed inclaim 1, wherein the carbon number of the α-olefin is any of 4 to 8.